Process for the preparation of 3-aryl-benzofuran-2-ones

ABSTRACT

The instant invention discloses a process for the preparation of compounds of formula I  
                 
 
     wherein the general symbols are as defined in claim  1,  which process comprises hydrolyzing a compound of formula V  
                 
 
     wherein the general symbols are as defined in claim  1,  in an aqueous solvent in the presence of an acid. The compounds of the formula V are new and useful as stabilizers for protecting organic materials, in particular polymers and lubricants, against oxidative, thermal or light-induced degradation.

[0001] Process for the preparation of 3-aryl-benzofuran-2-ones

[0002] The present invention relates to a novel process for thepreparation of 3-aryl-benzofuran-2-ones starting from new2-amino-benzofuranes, both of which are suitable for stabilising organicmaterials against oxidative, thermal or light-induced degradation.

[0003] The best processes hitherto for the preparation of3-aryl-benzofuran-2-ones are described, for example, in U.S. Pat. No.4,325,863; U.S. Pat. No. 5,607,624 and WO-A-99/67232.

[0004] The process disclosed in U.S. Pat. No. 4,325,863 (Example 1,column 8, lines 35-45) for the preparation of3-phenyl-3H-benzofuran-2-ones, for example5,7-di-tert-butyl-3-phenyl-3H-benzofuran-2-one of formula C, comprisesreacting the 2,4-di-tert-butylphenol of formula A with the mandelic acidof formula B, with removal of water.

[0005] A disadvantage of that process is that it requires the use ofmandelic acids substituted on the phenyl ring or heterocyclic mandelicacids. Not very many of those mandelic acids are known from theliterature, however, and the known synthesis procedures for thepreparation thereof are relatively complicated.

[0006] The process disclosed in U.S. Pat. No. 5,607,624 (Example 1,column 24) for the preparation of 3-phenyl-3H-benzofuran-2-onessubstituted on the 3-phenyl ring, for example5,7-di-tert-butyl-3-(2,5-dimethyl-phenyl)-3H-benzofuran-2-one of formulaF, comprises reacting the5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one of formula D withp-xylene of formula E, with removal of water.

[0007] A disadvantage of that process is that, for the preparation ofunsubstituted 3-phenyl-benzo-furanone derivatives, it requires the useof benzene, which is carcinogenic, instead of p-xylene.

[0008] The process disclosed in WO-A-99/67232 (Example 2, page 35) forthe preparation of 3-phenyl-3H-benzofuran-2-ones, for example5,7-di-tert-butyl-3-phenyl-3H-benzofuran-2-one of formula C, comprisesreacting a compound of formula G with carbon monoxide in the presence ofa catalyst.

[0009] A disadvantage of that process is that it requires the use of arelatively expensive catalyst.

[0010] There is therefore still a need to find an efficient process forthe preparation of 3-aryl-benzo-furan-2-ones that does not have thedisadvantages mentioned above.

[0011] The present invention therefore relates to a process for thepreparation of compounds of formula I

[0012] wherein, when n is 1,

[0013] R₁ is naphthyl, phenanthryl, anthryl,5,6,7,8-tetrahydro-2-naphthyl, thienyl, benzo[b]thienyl,naphtho[2,3-b]thienyl, thianthrenyl, furyl, benzofuryl, isobenzofuryl,dibenzofuryl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl,pyrazolyl, pyrazinyl, pyridyl, pyrimidinyl, pyridazinyl, indolizinyl,isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl,quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl,cinnolinyl, pteridinyl, carbazolyl, p-carbolinyl, phenanthridinyl,acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl,phenothiazinyl, isoxazolyl, furazanyl, biphenyl, terphenyl, fluorenyl orphenoxazinyl, each of which is unsubstituted or substituted by fluorine,hydroxy, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, C₁-C₁₈alkylthio,di-(C₁-C₄alkyl)amino, phenyl, benzyl, benzoyl or by benzoyloxy or R₁ isa radical of formula II or III

[0014] when n is 2,

[0015] R₁ is phenylene or naphthylene each unsubstituted or substitutedby C₁-C₄alkyl or by fluorine; or is —R₆—X—R₇—, R₂, R₃, R₄ and R₅ areeach independently of the others hydrogen, fluorine, hydroxy,C₁-C₂₅-alkyl, C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substitutedphenyl, unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl;C₁-C₁₈alkoxy, C₁-C₁₈alkylthio, C₁-C₄alkylamino, di-(C₁-C₄alkyl)amino,C₁-C₂₅alkanoyloxy, C₁-C₂₅alkanoylamino; C₃-C₂₅alkanoyloxy interrupted byoxygen, sulfur or by

[0016] C₆-C₉cycloalkylcarbonyloxy, benzoyloxy or C₁-C₁₂alkyl-substitutedbenzoyloxy, or furthermore the radicals R₂ and R₃ or the radicals R₃ andR₄ or the radicals R₄ and R₅, together with the carbon atoms to whichthey are bonded, form a benzo ring, R₄ is additionally —(CH₂)_(p)—COR₉or —(CH₂)_(q)OH or, when R₃ and R₅ are hydrogen, R₄ is additionally aradical of formula IV

[0017] wherein R₁ is as defined above for the case where n=1,

[0018] R₆ and R₇ are each independently of the other phenylene ornaphthylene each unsubstituted or substituted by C₁-C₄alkyl,

[0019] R₈ is C₁-C₈alkyl,

[0020] R₉ is hydroxy,$\left\lbrack {{—O}^{-}\frac{1}{r}M^{r +}} \right\rbrack,$

[0021] C₁-C₁₈alkoxy or

[0022] R₁₀ and R₁₁ are each independently of the other hydrogen, CF₃,C₁-C₁₂alkyl or phenyl, or R₁₀ and R₁₁ , together with the carbon atom towhich they are bonded, form a C₅-C₈cycloalkyl-idene ring unsubstitutedor substituted by from 1 to 3 C₁-C₄alkyl groups;

[0023] R₁₂ and R₁₃ are each independently of the other hydrogen orC₁-C₁₈alkyl,

[0024] R₁₄ is hydrogen or C₁-C₁₈alkyl,

[0025] R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ are each independently of the othershydrogen, halogen, fluoro-substituted C₁-C₁₂alkyl; —CN,

[0026] —SO₂R₄₆, SO₃R₄₆, hydroxy, C₁-C₂₅alkyl; C₂-C₂₅alkyl interrupted byoxygen, sulfur or by

[0027] C₁-C₂₅alkoxy; C₂-C₂₅alkoxy interrupted by oxygen, sulfur or by

[0028] C₁-C₂₅alkylthio, C₇-C₉phenylalkyl, C₇-C₉phenylalkoxy,unsubstituted or C₁-C₄alkyl-substituted phenyl; unsubstituted orC₁-C₄alkyl-substituted phenoxy; unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkoxy; di(C₁-C₄alkyl)amino, C₁-C₂₅alkanoyl; C₃-C₂₅alkanoylinterrupted by oxygen, sulfur or by

[0029] C₁-C₂₅alkanoyloxy; C₃-C₂₅alkanoyloxy interrupted by oxygen,sulfur or by

[0030] C₁-C₂₅alkanoylamino, C₆-C₉cycloalkylcarbonyl,C₆-C₉cycloalkylcarbonyloxy, benzoyl or C₁-C₁₂alkyl-substituted benzoyl;benzoyloxy or C₁-C₁₂alkyl-substituted benzoyloxy;

[0031] R₂₄ is hydrogen, C₁-C₄alkyl, or unsubstituted orC₁-C₄alkyl-substituted phenyl,

[0032] R₂₅ and R₂₆ are hydrogen, C₁-C₄alkyl or phenyl, with the provisothat at least one of the radicals R₂₅ and R₂₆ is hydrogen,

[0033] R₂₇ and R₂₈ are each independently of the other hydrogen,C₁-C₄alkyl or phenyl, R₂₉ is hydrogen or C₁-C₄alkyl,

[0034] R₃₀ is hydrogen, unsubstituted or C₁-C₄alkyl-substituted phenyl;C₁-C₂₅alkyl; C₂-C₂₅alkyl interrupted by oxygen, sulfur or by

[0035] C₇-C₉phenylalkyl unsubstituted or substituted on the phenylradical by from 1 to 3 C₁-C₄alkyl grou ps; or C₇-C₂₅phenylalkylinterrupted by oxygen, sulfur or by

[0036] and unsubstituted or substituted on the phenyl radical by from 1to 3 C₁-C₄alkyl groups,

[0037] R₃₁ is hydrogen or C₁-C₄alkyl,

[0038] R₃₂ is hydrogen, C₁-C₂₅alkanoyl; C₃-C₂₅alkanoyl interrupted byoxygen, sulfur or by

[0039] C₂-C₂₅alkanoyl substituted by a di(C₁-C₆alkyl) phosphonate group;C₆-C₉-cycloalkylcarbonyl, thenoyl, furoyl, benzoyl orC₁-C₁₂alkyl-substituted benzoyl;

[0040] R₃₃ is hydrogen or C₁-C₈alkyl,

[0041] R₃₄ is a direct bond, C₁-C₁₈alkylene; C₂-C₁₈alkylene interruptedby oxygen, sulfur or by

[0042] C₂-C₂₀alkylidene, C₇-C₂₀phenylalkylidene, C₅-C₈cycloalkylene,C₇-C₈bicyclo-alkylene, unsubstituted or C₁-C₄alkyl-substitutedphenylene, or

[0043] R₃₅ is hydroxy,$\left\lbrack {{—O}^{-}\frac{1}{r}M^{r +}} \right\rbrack,$

[0044] C₁-C₁₈alkoxy or

[0045] R₃₆ is oxygen, —NH— or

[0046] R₃₇ is C₁-C₁₈alkyl or phenyl,

[0047] R₄₂ is hydrogen, hydroxy,$\left\lbrack {{—O}^{-}\frac{1}{r}M^{r +}} \right\rbrack,$

[0048] C₁-C₂₅alkyl, C₇-C₉phenylalkyl, unsubstituted orC₁-C₄alkyl-substituted phenyl; unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; or C₃-C₂₅alkyl which is interrupted by oxygen, sulfuror

[0049] R₄₃ is C₁-C₂₅alkyl, C₇-C₉phenylalkyl, unsubstituted orC₁-C₄alkyl-substituted phenyl; unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; or C₃-C₂₅alkyl which is interrupted by oxygen, sulfuror

[0050] R₄₄ and R₄₅ are each independently of one another hydrogen,C₁-C₂₅alkyl, hydroxyl-substituted C₂-C₂₄alkyl; C₃-C₂₅alkyl which isinterrupted by oxygen, sulfur or

[0051] phenylalkyl which is unsubstituted or is substituted on thephenyl ring by C₁-C₄alkyl; or C₃-C₂₄alkenyl; or R₄₄ and R₄₅, togetherwith the nitrogen atom to which they are attached, form a 5-, 6- or7-membered heterocyclic ring which is unsubstituted or is substituted byC₁-C₄alkyl or is interrupted by oxygen, sulfur or

[0052] R₄₆ is hydrogen or C₁-C₂₅alkyl,

[0053] M is an r-valent metal cation,

[0054] X is a direct bond, oxygen, sulfur or —NR₁₄—,

[0055] n is 1 or 2,

[0056] p is 0, 1 or2,

[0057] q is 1, 2, 3, 4, 5 or 6,

[0058] r is 1, 2 or 3, and

[0059] s is 0, 1 or 2,

[0060] which process comprises hydrolyzing a compound of formula V

[0061] wherein

[0062] R₁ and n are as defined above,

[0063] R₂, R₃, R′₄ and R₅ are each independently of the others hydrogen,fluorine, hydroxy, C₁-C₂₅alkyl, C₇-C₉phenylalkyl, unsubstituted orC₁-C₄alkyl-substituted phenyl, unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈-cycloalkyl; C₁-C₁₈alkoxy, C₁-C₁₈alkylthio, C₁-C₄alkylamino,di(C₁-C₄alkyl)amino, C₁-C₂₅alkanoyloxy, C₁-C₂₅alkanoylamino;C₃-C₂₅alkanoyloxy interrupted by oxygen, sulfur or by

[0064] C₆-C₉cycloalkylcarbonyloxy, benzoyloxy or C₁-C₁₂alkyl-substitutedbenzoyloxy, or furthermore the radicals R₂ and R₃ or the radicals R₃ andR′₄ or the radicals R′₄ and R₅, together with the carbon atoms to whichthey are bonded, form a benzo ring, R′₄ is additionally —(CH₂)p—COR₉ or—(CH₂)_(q)OH or, when R₃ and R₅ are hydrogen, R′₄ is additionally aradical of formula VI

[0065] wherein R₁ is as defined above for the case where n=1, in anaqueous solvent in the presence of an acid.

[0066] Alkanoyl having up to 25 carbon atoms is a branched or unbranchedradical, for example formyl, acetyl, propionyl, butanoyl, pentanoyl,hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl,dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl,heptadecanoyl, octadecanoyl, icosanoyl or docosanoyl. Alkanoyl haspreferably from 2 to 18, especially from 2 to 12, e.g. from 2 to 6,carbon atoms. Special preference is given to acetyl.

[0067] C₂-C₂₅Alkanoyl substituted by a di(C₁-C₆alkyl) phosphonate groupis, for example,

[0068] (CH₃CH₂O)₂POCH₂CO—, (CH₃O)₂POCH₂CO—, (CH₃CH₂CH₂CH₂O)₂POCH₂CO—,

[0069] (CH₃CH₂O)₂POCH₂CH₂CO—, (CH₃O)₂POCH₂CH₂CO—,(CH₃CH₂CH₂CH₂O)₂POCH₂CH₂CO—,

[0070] (CH₃CH₂O)₂PO(CH₂)₄CO—, (CH₃CH₂O)₂PO(CH₂)₈CO— or(CH₃CH₂O)₂PO(CH₂)₁₇CO—.

[0071] Alkanoyloxy having up to 25 carbon atoms is a branched orunbranched radical, for example formyloxy, acetoxy, propionyloxy,butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy,nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy, tridecanoyloxy,tetradecanoyloxy, pentadecanoyloxy, hexadecanoyloxy, heptadecanoyloxy,octadecanoyloxy, icosanoyloxy or docosanoyloxy. Preference is given toalkanoyloxy having from 2 to 18, especially from 2 to 12, e.g. from 2 to6, carbon atoms. Special preference is given to acetoxy.

[0072] C₃-C₂₅Alkenoyloxy interrupted by oxygen, sulfur or by

[0073] is, for example, CH₃OCH₂CH₂CH═CHCOO— or CH₃OCH₂CH₂OCH═CHCOO—.

[0074] C₃-C₂₅Alkanoyl interrupted by oxygen, sulfur or by

[0075] is, for example,

[0076] CH₃—O—CH₂CO—, CH₃—S—CH₂CO—, CH₃—N(CH₃)—CH₂CO—,CH₃—O—CH₂CH₂—O—CH₂CO—,

[0077] CH₃—(O—CH₂CH₂—)₂O—CH₂CO—, CH₃—(O—CH₂CH₂—)₃O—CH₂CO— or

[0078] CH₃—(O—CH₂CH₂—)₄O—CH₂CO—.

[0079] C₃-C₂₅Alkanoyloxy interrupted by oxygen, sulfur or by

[0080] is, for example,

[0081] CH₃—O—CH₂COO—, CH₃—S—CH₂COO—, CH₃—N(CH₃)—CH₂COO—,

[0082] CH₃—O—CH₂CH₂—O—CH₂COO—, CH₃—(O—CH₂CH₂—)₂O—CH₂COO—,

[0083] CH₃—(O—CH₂CH₂—)₃O—CH₂COO— or CH₃—(O—CH₂CH₂—)₄O—CH₂COO—.

[0084] C₆-C₉Cycloalkylcarbonyl is, for example, cyclopentylcarbonyl,cyclohexylcarbonyl, cycloheptylcarbonyl or cyclooctylcarbonyl.Preference is given to cyclohexylcarbonyl.

[0085] C₆-C₉Cycloalkylcarbonyloxy is, for example,cyclopentylcarbonyloxy, cyclohexylcarbonyloxy, cycloheptylcarbonyloxy orcyclooctylcarbonyloxy. Preference is given to cyclohexylcarbonyloxy.

[0086] C₁-C₁₂Alkyl-substituted benzoyl, which carries preferably from 1to 3, especially 1 or 2, alkyl groups, is, for example, o-, m- orp-methylbenzoyl, 2,3-dimethylbenzoyl, 2,4-dimethyl-benzoyl,2,5-dimethylbenzoyl, 2,6-dimethylbenzoyl, 3,4-dimethylbenzoyl,3,5-dimethyl-benzoyl, 2-methyl-6-ethylbenzoyl, 4-tert-butylbenzoyl,2-ethylbenzoyl, 2,4,6-trimethylbenzoyl, 2,6-dimethyl-4-tert-butylbenzoylor 3,5-di-tert-butylbenzoyl. Preferred substituents are C₁-C₈-alkyl,especially C₁-C₄alkyl.

[0087] C₁-C₁₂Alkyl-substituted benzoyloxy, which carries preferably from1 to 3, especially 1 or 2, alkyl groups, is, for example, o-, m- orp-methylbenzoyloxy, 2,3-dimethylbenzoyloxy, 2,4-di-methylbenzoyloxy,2,5-dimethylbenzoyloxy, 2,6-dimethylbenzoyloxy, 3,4-dimethylbenzoyloxy,3,5-dimethylbenzoyloxy, 2-methyl-6-ethylbenzoyloxy,4-tert-butylbenzoyloxy, 2-ethylbenzoyl-oxy, 2,4,6-trimethylbenzoyloxy,2,6-dimethyl-4-tert-butylbenzoyloxy or 3,5-di-tert-butylbenzoyloxy.Preferred substituents are C₁-C₈alkyl, especially C₁-C₄alkyl.

[0088] Alkyl having up to 25 carbon atoms is a branched or unbranchedradical, for example methyl, ethyl, propyl, isopropyl, n-butyl,sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl,1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl,isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl,n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl,nonyl, decyl, undecyl, 1-methylundecyl, dodecyl,1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, icosyl or docosyl. One of thepreferred definitions for R₂ and R₄ is, for example, C₁-C₁₈alkyl. Anespecially preferred definition for R₄ is C₁-C₄alkyl.

[0089] C₂-C₂₅Alkyl interrupted by oxygen, sulfur or by

[0090] is, for example, CH₃—O—CH₂—, CH₃—S—CH₂—, CH₃—N(CH₃)—CH₂—,CH₃—O—CH₂CH₂—O—CH₂—, CH₃—(O—CH₂CH₂—)₂O—CH₂—, CH₃—(O—CH₂CH₂—)₃O—CH₂— orCH₃—(O—CH₂CH₂—)₄O—CH₂—.

[0091] C₇-C₉Phenylalkyl is, for example, benzyl, α-methylbenzyl,α,α-dimethylbenzyl or 2-phenyl-ethyl. Preference is given to benzyl andα,α-dimethylbenzyl.

[0092] C₇-C₉Phenylalkyl unsubstituted or substituted on the phenylradical by from 1 to 3 C₁-C₄alkyl groups is, for example, benzyl,α-methylbenzyl, α,α-dimethylbenzyl, 2-phenylethyl, 2-methylbenzyl,3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 2,6-dimethylbenzylor 4-tertbutylbenzyl. Preference is given to benzyl.

[0093] C₇-C₂₅Phenylalkyl interrupted by oxygen, sulfur or by

[0094] and unsubstituted or substituted on the phenyl radical by from 1to 3 C₁-C₄alkyl groups is a branched or unbranched radical, for examplephenoxymethyl, 2-methyl-phenoxymethyl, 3-methyl-phenoxymethyl,4-methyl-phenoxymethyl, 2,4-dimethyl-phenoxymethyl,2,3-dimethyl-phenoxymethyl, phenylthiomethyl,N-methyl-N-phenyl-aminomethyl, N-ethyl-N-phenyl-aminomethyl,4-tert-butyl-phenoxymethyl, 4-tert-butyl-phenoxyethoxy-methyl,2,4-di-tert-butyl-phenoxymethyl, 2,4-di-tert-butyl-phenoxyethoxymethyl,phenoxyethoxyethoxyethoxym ethyl, benzyloxym ethyl,benzyloxyethoxymethyl, N-benzyl-N-ethyl-aminomethyl orN-benzyl-N-isopropyl-aminomethyl.

[0095] C₇-C₉Phenylalkoxy is, for example, benzyloxy, α-methylbenzyloxy,α,α-dimethylbenzyloxy or 2-phenylethoxy. Preference is given tobenzyloxy.

[0096] C₁-C₄Alkyl-substituted phenyl, which contains preferably from 1to 3, especially 1 or 2, alkyl groups, is, for example, o-, m- orp-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl,2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl,3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl,2-ethylphenyl or 2,6-diethylphenyl.

[0097] C₁-C₄Alkyl-substituted phenoxy, which contains preferably from 1to 3, especially 1 or 2, alkyl groups, is, for example, o-, m- orp-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy,2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy,3,5-dimethylphenoxy, 2-methyl-6-ethylphenoxy, 4-tert-butylphenoxy,2-ethylphenoxy or 2,6-diethylphenoxy.

[0098] Unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl is, forexample, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl,cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl,tert-butylcyclohexyl, cycloheptyl or cyclooctyl. Preference is given tocyclohexyl and tert-butylcyclohexyl.

[0099] Unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkoxy is, forexample, cyclopentyloxy, methylcyclopentyloxy, dimethylcyclopentyloxy,cyclohexyloxy, methylcyclohexyloxy, dimethylcyclohexyloxy,trimethylcyclohexyloxy, tert-butylcyclohexyloxy, cycloheptyloxy orcyclooctyloxy. Preference is given to cyclohexyloxy andtert-butylcyclohexyloxy.

[0100] Alkoxy having up to 25 carbon atoms is a branched or unbranchedradical, for example methoxy, ethoxy, propoxy, isopropoxy, n-butoxy,isobutoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy,decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy. Preference isgiven to alkoxy having from 1 to 12, especially from 1 to 8, e.g. from 1to 6, carbon atoms.

[0101] C₂-C₂₅Alkoxy interrupted by oxygen, sulfur or by

[0102] is, for example,

[0103] CH₃—O—CH₂CH₂O—, CH₃—S—CH₂CH₂O—, CH₃—N(CH₃)—CH₂CH₂O—,

[0104] CH₃—O—CH₂CH₂—O—CH₂CH₂O—, CH₃—(O—CH₂CH₂—)₂O—CH₂CH₂O—,

[0105] CH₃—(O—CH₂CH₂—)₃O—CH₂CH₂O— or CH₃—(O—CH₂CH₂—)₄O—CH₂CH₂O—.

[0106] Alkylthio having up to 25 carbon atoms is a branched orunbranched radical, for example methylthio, ethylthio, propylthio,isopropylthio, n-butylthio, isobutylthio, pentylthio, isopentylthio,hexylthio, heptylthio, octylthio, decylthio, tetradecylthio,hexadecylthio or octadecylthio. Preference is given to alkylthio havingfrom 1 to 12, especially from 1 to 8, e.g. from 1 to 6, carbon atoms.

[0107] Alkylamino having up to 4 carbon atoms is a branched orunbranched radical, for example methylamino, ethylamino, propylamino,isopropylamino, n-butylamino, isobutylamino or tertbutylamino.

[0108] Di(C₁-C₄alkyl)amino means also that the two radicals are eachindependently of the other branched or unbranched, for example,dimethylamino, methylethylamino, diethylamino, methyl-n-propylamino,methylisopropylamino, methyl-n-butylamino, methylisobutylamino,ethylisopropylamino, ethyl-n-butylamino, ethylisobutylamino,ethyl-tert-butylamino, diethylamino, diisopropylamino,isopropyl-n-butylamino, isopropylisobutylamino, di-n-butylamino ordi-isobutylamino.

[0109] Alkanoylamino having up to 25 carbon atoms is a branched orunbranched radical, for example formylamino, acetylamino,propionylamino, butanoylamino, pentanoylamino, hexanoylamino,heptanoylamino, octanoylamino, nonanoylamino, decanoylamino,undecanoyl-amino, dodecanoylamino, tridecanoylamino, tetradecanoylamino,pentadecanoylamino, hexadecanoylamino, heptadecanoylamino,octadecanoylamino, icosanoylamino or docosanoylamino. Preference isgiven to alkanoylamino having from 2 to 18, especially from 2 to 12,e.g. from 2 to 6, carbon atoms.

[0110] C₁-C₁₈Alkylene is a branched or unbranched radical, for examplemethylene, ethylene, propylene, trimethylene, tetramethylene,pentamethylene, hexamethylene, heptamethylene, octamethylene,decamethylene, dodecamethylene or octadecamethylene. Preference is givento C₁-C₁₂alkylene, especially C₁-C₈alkylene. An especially preferreddefinition for R₅₆ is C₂-C₈alkylene, especially C₄-C₈alkylene, forexample tetramethylene or pentamethylene.

[0111] C₂-C₁₈Alkylene interrupted by oxygen, sulfur or by

[0112] is, for example,

[0113] —CH₂—O—CH₂—, —CH₂—S—CH₂—, —CH₂—N(CH₃)—CH₂—, —CH₂—O—CH₂CH₂—O—CH₂—,

[0114] —CH₂—(O—CH₂CH₂—)₂O—CH₂—, —CH₂—(O—CH₂CH₂—)₃O—CH₂—,—CH₂—(O—CH₂CH₂—)₄O—CH₂— or

[0115] —CH₂CH₂—S—CH₂CH₂—,

[0116] Alkylidene having from 2 to 20 carbon atoms is, for example,ethylidene, propylidene, butylidene, pentylidene, 4-methylpentylidene,heptylidene, nonylidene, tridecylidene, nonadecyl-, idene,1-methylethylidene, 1-ethylpropylidene or 1-ethylpentylidene. Preferenceis given to C₂-C₈alkylidene.

[0117] Phenylalkylidene having from 7 to 20 carbon atoms is, forexample, benzylidene, 2-phenyl-ethylidene or 1-phenyl-2-hexylidene.Preference is given to C₇-C₉phenylalkylidene.

[0118] C₅-C₈Cycloalkylene is a saturated hydrocarbon group having twofree valences and at least one ring unit and is, for example,cyclopentylene, cyclohexylene, cycloheptylene or cyclooctylene.Preference is given to cyclohexylene.

[0119] C₇-C₈Bicycloalkylene is, for example, bicycloheptylene orbicyclooctylene.

[0120] Phenylene or naphthylene each unsubstituted or substituted byC₁-C₄alkyl is, for example, 1,2-, 1,3- or 1,4-phenylene or 1,2-, 1,3-,1,4-, 1,6-, 1,7-, 2,6- or 2,7-naphthylene. Preference is given to1,4-phenylene.

[0121] A C₅-C₈cycloalkylidene ring substituted by C₁-C₄alkyl, whichcontains preferably from 1 to 3, especially 1 or 2, branched orunbranched alkyl group radicals, is, for example, cyclopentylidene,methylcyclopentylidene, dimethylcyclopentylidene, cyclohexylidene,methylcyclohexylidene, dimethylcyclohexylidene,trimethylcyclohexylidene, tert-butylcyclohexylidene, cycloheptylidene orcyclooctylidene. Preference is given to cyclohexylidene andtert-butylcyclo-hexylidene.

[0122] A mono-, di- or tri-valent metal cation is preferably an alkalimetal cation, alkaline earth metal cation or aluminium cation, forexample Na⁺, K⁺, Mg⁺⁺, Ca⁺⁺ or Al⁺⁺⁺.

[0123] Dendrimeric, oligomeric or polymeric C₄-C₁₀₀hydrocarbon radicalsare, for example, those such as are disclosed by R. Mülhaupt et al. inAngew. Chem., Int. Ed. 32 (9), 1306 (1993).

[0124] Halogen is, for example, chlorine, bromine or iodine. Preferenceis given to chlorine and bromine.

[0125] Fluoro-substituted C₁-C₁₂alkyl is a branched or unbranchedradical, for example fluoromethyl, difluoromethyl, trifluoromethyl orpentafluoroethyl. Trifluoromethyl is preferred.

[0126] Hydroxyl-substituted C₂-C₂₄alkyl is a branched or unbranchedradical which contains preferably 1 to 3, in particular 1 or 2, hydroxylgroups, such as, for example, hydroxyethyl, 3-hydroxypropyl,2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl,5-hydroxypentyl, 4-hydroxypentyl, 3-hydroxypentyl, 2-hydroxypentyl,6-hydroxyhexyl, 5-hydroxyhexyl, 4-hydroxyhexyl, 3-hydroxyhexyl,2-hydroxyhexyl, 7-hydroxyheptyl, 6-hydroxyheptyl, 5-hydroxyheptyl,4-hydroxyheptyl, 3-hydroxyheptyl, 2-hydroxyheptyl, 8-hydroxyoctyl,7-hydroxyoctyl, 6-hydroxyoctyl, 5-hydroxyoctyl, 4-hydroxyoctyl,3-hydroxyoctyl, 2-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl,11-hydroxyundecyl, 12-hydroxydodecyl, 13-hydroxytridecyl,14-hydroxytetradecyl, 15-hydroxypentadecyl, 1 6-hydroxyhexadecyl, 17-hydroxyheptadecyl, 1 8-hydroxyoctadecyl, 20-hydroxyeicosyl or22-hydroxydocosyl. A preferred definition of R₄₄ and R₄₅ ishydroxyl-substituted C₂-C₂₀alkyl, especially hydroxyl-substitutedC₂-C₁₈alkyl, for example hydroxyl-substituted C₂-C₁₄alkyl. Aparticularly preferred definition of R₄₄ and R₄₅ is hydroxyl-substitutedC₂-C₁₂alkyl, especially hydroxyl-substituted C₂-C₈alkyl, for examplehydroxyl-substituted C₂-C₄alkyl, such as 2-hydroxyethyl, for example.

[0127] Where R₄₄ and R₄₅ together with the nitrogen atom to which theyare attached, form a 5-, 6- or 7-membered heterocyclic ring which isunsubstituted or is substituted by C₁-C₄alkyl or is interrupted byoxygen, sulfur or

[0128] this denotes, for example, the following radicals:

[0129] R₄₅ or R₂₇ preferably form, with the nitrogen atom to which theyare attached, a 6-membered heterocyclic ring interrupted by oxygen, suchas, for example,

[0130] Of interest is a process for the preparation of compounds offormula I wherein, when n is 2,

[0131] R₁ is phenylene or —R₆—X—R₇—,

[0132] R₆ and R₇ are phenylene,

[0133] X is oxygen or —NR₁₄—, and

[0134] R₁₄ is C₁-C₄alkyl.

[0135] Likewise of interest is a process for the preparation ofcompounds of formula I wherein R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ are eachindependently of the others hydrogen, chloro, bromo, fluoro-substitutedC₁-C₁₂alkyl; —CN,

[0136] —SOR₄₆, —SO₂R₄₆, SO₃R₄₆, hydroxy, C₁-C₁₈alkyl; C₂-C₁₈alkylinterrupted by oxygen or by sulfur; C₁-C₁₈alkoxy; C₂-C₁₈alkoxyinterrupted by oxygen or by sulfur; C₁-C₁₈alkylthio, C₇-C₉phenylalkyl,C₇-C₉phenylalkoxy, unsubstituted or C₁-C₄alkyl substituted phenyl;phenoxy, cyclohexyl, C₅-C₈cycloalkoxy, di(C₁-C₄alkyl)amino,C₁-C₁₂alkanoyl; C₃-C₁₂alkanoyl interrupted by oxygen or by sulfur;C₁-C₁₂alkanoyloxy; C₃-C₁₂alkanoyloxy interrupted by oxygen or by sulfur;C₁-C₁₂alkanoylamino, cyclohexylcarbonyl, cyclohexylcarbonyloxy, benzoylor C₁-C₄alkyl-substituted benzoyl; benzoyloxy or C₁-C₄alkyl-substitutedbenzoyloxy;

[0137] R₂₄ is hydrogen or C₁-C₄alkyl,

[0138] R₂₅ and R₂₆ are hydrogen or C₁-C₄alkyl, with the proviso that atleast one of the radicals R₂₅ and R₂₆ is hydrogen,

[0139] R₂₇ and R₂₈ are each independently of the other hydrogen orC₁-C₄alkyl,

[0140] R₂₉ is hydrogen,

[0141] R₃₀ is hydrogen, phenyl, C₁-C₁₈alkyl; C₂-C₁₈alkyl interrupted byoxygen or by sulfur; C₇-C₉-phenylalkyl; or C₇-C₁₈phenylalkyl interruptedby oxygen or by sulfur and unsubstituted or substituted on the phenylradical by from 1 to 3 C₁-C₄alkyl groups,

[0142] R₃₁ is hydrogen or C₁-C₄alkyl,

[0143] R₃₂ is hydrogen, C₁-C₁₈alkanoyl; C₃-Cl₂alkanoyl interrupted byoxygen or by sulfur; C₂-C₁₂-alkanoyl substituted by a di(C₁-C₆alkyl)phosphonate group; C₆-C₉cycloalkylcarbonyl, benzoyl,

[0144] R₃₃ is hydrogen or C₁-C₄alkyl,

[0145] R₃₄ is C₁-C₂alkylene, C₂-C₈alkylidene, C₇-C₁₂phenylalkylidene,C₅-C₈cycloalkylene or phenylene,

[0146] R₃₅ is hydroxy,$\left\lbrack {{—O}^{-}\frac{1}{r}M^{r +}} \right\rbrack$

[0147] or C₁-C₁₈alkoxy,

[0148] R₃₆ is oxygen or —NH—,

[0149] R₃₇ is C₁-C₈alkyl or phenyl,

[0150] R₄₂ is hydrogen, hydroxy, C₁-C₁₈alkyl, C₇-C₉phenylalkyl,unsubstituted or C₁-C₄alkyl-substituted phenyl; C₅-C₈cycloalkyl; orC₃-C₂₅alkyl which is interrupted by oxygen or sulfur,

[0151] R₄₃ is C₁-C₁₈alkyl, C₇-C₉phenylalkyl, unsubstituted orCl-C₄alkyl-substituted phenyl; C₅-C₈cycloalkyl; or C₃-C₁₈alkyl which isinterrupted by oxygen or sulfur,

[0152] R₄₄ and R₄₅ are each independently of one another hydrogen,Cl-C,₈alkyl, hydroxyl-substituted C₂-C₁₈alkyl; C₃-C18alkyl which isinterrupted by oxygen or sulfur; C₇-C₉-phenylalkyl, or C₃-C₁₈alkenyl; orR₄₄ and R₄₅, together with the nitrogen atom to which they are attached,form a 6-membered heterocyclic ring,

[0153] R₄₆ is C₁-C₁₈alkyl, and

[0154] s is1 or2.

[0155] Of special interest is a process for the preparation of compoundsof formula I wherein, when n is 1,

[0156] R₁ is naphthyl, phenanthryl, thienyl, pyridyl, dibenzofuryl,unsubstituted or C₁-C₄alkyl-substituted carbazolyl; or fluorenyl, or R₁is a radical of formula II

[0157] when n is 2,

[0158] R₁ is phenylene or naphthylene;

[0159] R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ are each independently of the othershydrogen, chloro, bromo, fluoro-substituted C₁-C₈alkyl; —CN,

[0160] hydroxy, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, C₁-C₁₈alkylthio, phenyl,benzoyl, benzoyloxy or

[0161] R₂₉ is hydrogen,

[0162] R₃₀ is hydrogen, phenyl or C₁-C₁₈alkyl,

[0163] R₃₁ is hydrogen or C₁-C₄alkyl,

[0164] R₃₂ is hydrogen, C₁-C₁₂alkanoyl or benzoyl, and

[0165] R₄₃ is C₁-C₁₈alkyl, benzyl, phenyl; cyclohexyl; or C₃-C₁₂alkylwhich is interrupted by oxygen, and

[0166] R₄₄ and R₄₅ are each independently of one another hydrogen,C₁-C₁₄alkyl, hydroxyl-substituted C₂-C₁₄alkyl; C₃-C₁₂alkyl which isinterrupted by oxygen; benzyl or C₃-C₁₂alkenyl.

[0167] Likewise of special interest is a process for the preparation ofcompounds of formula I wherein

[0168] R₁₉ is hydrogen, hydroxy, bromo, trifluoromethyl, C₁-C₄alkyl orC₁-C₄alkoxy,

[0169] R₂₀ is hydrogen, bromo, trifluoromethyl, C₁-C₄alkyl orC₁-C₄alkoxy,

[0170] R₂₁ is hydrogen, bromo, trifluoromethyl, C₁-C₄alkyl, C₁-C₄alkoxy,C₁-C₄alkylthio,

[0171] R₂₂ is hydrogen, bromo, trifluoromethyl, C₁-C₄alkyl orC₁-C₄alkoxy, and

[0172] R₂₃ is hydrogen, hydroxy, bromo, trifluoromethyl, C₁-C₄alkyl orC₁-C₄alkoxy.

[0173] Of special interest is, more especially, a process for thepreparation of compounds of formula I wherein

[0174] R₂, R₃, R₄ and R₅ are each independently of the others hydrogen,fluorine, hydroxy, C₁-C₂₅-alkyl, C₇-C₉phenylalkyl, unsubstituted orC₁-C₄alkyl-substituted phenyl; unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; C₁-C₁₂alkoxy, C₁-C₁₂alkylthio, C₁-C₄alkylamino,di-(C₁-C₄alkyl)amino, C₁-C₁₈alkanoyloxy, C₁-C₁₈alkanoylamino;C₃-C₁₈alkanoyloxy interrupted by oxygen, sulfur or by

[0175] C₆-C₉cycloalkylcarbonyloxy, benzoyloxy or C₁-C₈alkyl-substitutedbenzoyloxy, or furthermore the radicals R₂ and R₃ or the radicals R₃ andR₄ or the radicals R₄ and R₅, together with the carbon atoms to whichthey are bonded, form a benzo ring, R₄ is additionally —(CH₂)_(p)—COR₉or —(CH₂)_(q)OH or, when R₃ and R₅ are hydrogen, R₄ is additionally aradical of formula IV

[0176] R₈ is C₁-C₆alkyl,

[0177] R₉ is hydroxy, C₁-C₁₈alkoxy or

[0178] R₁₀ and R₁₁ are methyl groups or, together with the carbon atomto which they are bonded, form a C₅-C₈cycloalkylidene ring unsubstitutedor substituted by from 1 to 3 C₁-C₄alkyl groups;

[0179] R₁₂ and R₁₃ are each independently of the other hydrogen orC₁-C₈alkyl, and q is 2, 3, 4, 5 or 6.

[0180] Special preference is given to a process for the preparation ofcompounds of formula I wherein at least two of the radicals R₂, R₃, R₄and R₅ are hydrogen.

[0181] Also very especially preferred is a process for the preparationof compounds of formula I wherein R₃ and R₅ are hydrogen.

[0182] Very special preference is given to a process for the preparationof compounds of formula I wherein

[0183] R₂, R₃, R₄ and R₅ are each independently of the others hydrogen,fluorine, hydroxy, C₁-C₁₈-alkyl, C₇-C₉phenylalkyl, phenyl,C₅-C₈cycloalkyl, C₁-C₆alkoxy, cyclohexylcarbonyloxy or benzoyloxy, orfurthermore the radicals R₂ and R₃ or the radicals R₃ and R₄ or theradicals R₄ and R₅, together with the carbon atoms to which they arebonded, form a benzo ring, R₄ is additionally —(CH₂)_(p)—COR₉, or, whenR₃ and R₅ are hydrogen, R₄ is additionally a radical of formula IV,

[0184] R₉ is hydroxy or C₁-C₁₈alkoxy, and

[0185] R₁₀ and R₁₁ are methyl groups or, together with the carbon atomto which they are bonded, form a C₅-C₈cycloalkylidene ring.

[0186] Of preferential interest is a process for the preparation ofcompounds of formula I wherein R₂ is C₁-C₁₈alkyl or cyclohexyl,

[0187] R₃ is hydrogen,

[0188] R₄ is C₁-C₄alkyl, cyclohexyl, —(CH₂)_(p)—COR₉ or a radical offormula IV,

[0189] R₅ is hydrogen,

[0190] R₉ is C₁-C₄alkyl,

[0191] R₁₀ and R₁₁, together with the carbon atom to which they arebonded, form a cyclohexylidene ring, and

[0192] p is 2.

[0193] Preferred reaction conditions for the process according to theinvention are as follows:

[0194] The reaction may be carried out at an elevated temperature,especially at temperatures of from 20 to 200° C., especially of from 20to 150° C., e.g. from 20 to 80° C., in an aqueous solvent, optionallyunder slight pressure.

[0195] Preferred aqueous solvents are for example aqueous alcohols,aqueous dimethyl sulfoxide, aqueous sulfolane, aqueous dimethylformamide, aqueous tetrahydrofurane or aqueous dioxane. Aqueous alcoholsare especially preferred.

[0196] Especially preferred aqueous alcohols are C₁-C₁₂alcohols orC₁-C₁₂alcohols interrupted by oxygen. Examples of such alcoholsmethanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol,tert-butanol, n-pentanol, glycol, glycerol, ethylene glycol ordiethylene glycol.

[0197] Preferred acids are for example hydrochloric acid, hydrobromicacid, sulfuric acid, nitric acid phosphoric acid, sulfonic acids orcarboxylic acids. Hydrochloric acid is especially preferred.

[0198] Preferred sulfonic acids are for example methane sulfonic acid orp-toluene sulfonic acid. Preferred carboxylic acids are for exampleformic acid, acetic acid, propionic acid, trifluoroacetic acid, oxalicacid or phthalic acid.

[0199] The acid is preferably used in at least an equal molar amount inrespect to the compound of the formula V. Preferably, the molar ratiobetween the acid and the compound of the formula V is 4:1 to 1:1;especially 2:1 to 1:1, for example 1.3: 1 to 1:1.

[0200] The starting compounds of formula V are new and can be preparedfor example by the following new process.

[0201] The present invention therefore relates also to a preferredprocess for the preparation of the starting compounds of formula V

[0202] wherein the general symbols are as defined above, comprisesconverting a compound of formula VlI

[0203] wherein R₁ and n are as defined above,

[0204] R₂, R₃, R″₄ and R₅ are each independently of the others hydrogen,fluorine, hydroxy, C₁-C₂₅-alkyl, C₇-C₉phenylalkyl, unsubstituted orC₁-C₄alkyl-substituted phenyl, unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; C₁-C₁₈alkoxy, C₁-C₁₈alkylthio, C₁-C₄alkylamino,di(C₁-C₄alkyl)amino, C₁-C₂₅alkanoyloxy, C₁-C₂₅alkanoylamino;C₃-C₂₅alkanoyloxy interrupted by oxygen, sulfur or by

[0205] C₆-C₉cycloalkylcarbonyloxy, benzoyloxy or C₁-C₁₂alkyl-substitutedbenzoyloxy, or furthermore the radicals R₂ and R₃ or the radicals R₃ andR″₄ or the radicals R″₄ and R₅, together with the carbon atoms to whichthey are bonded, form a benzo ring, R″₄ is additionally —(CH₂)_(p)—COR₉or —(CH₂)₉OH or, when R₃ and R₅ are hydrogen, R″₄ is additionally aradical of formula VIII

[0206] wherein R₁ is as defined above for the case where n=1, R₂, R₁₀and R₁₁ are as defined above,

[0207] R₅₀ is —OR₅₁, —SR₅₂,

[0208] R₅₁ is C₁-C₂₅alkyl; C₂-C₂₅alkyl interrupted by oxygen or bysulfur; C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; unsubstituted or C₁-C₄alkyl-substituted phenyl,

[0209] R₅₂ is C₁-C₂₅alkyl; C₂-C₂₅alkyl interrupted by oxygen or bysulfur; C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; unsubstituted or C₁-C₄alkyl-substituted phenyl,

[0210] R₅₃ and R₅₄ are each independently of the other hydrogen,C₁-C₂₅alkyl; C₂-C₂₅alkyl interrupted by oxygen or by sulfur;C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈-cycloalkyl; or a dendrimeric, oligomeric or polymericC₄-C₁₀₀hydrocarbon radical,

[0211] R₅₅ is C₁-C₂₅alkyl; C₂-C₂₅alkyl interrupted by oxygen or bysulfur; C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; unsubstituted or C₁-C₄alkyl-substituted phenyl; or aradical of formula IX

[0212] wherein R₁, R₂, R₃, R″₄, R₅ and n are as defined above,

[0213] R₅₆ is unsubstituted or C₁-C₄alkyl-substituted C₂-C₁₂alkylene,with an aqueous cyanide salt solution.

[0214] Preferred reaction conditions for this process are as follows:

[0215] The reaction may be carried out at an elevated temperature,especially at temperatures of from 20 to 200° C., especially of from 50to 150° C, e.g. 80 to 130° C., in an solvent, optionally under slightpressure.

[0216] Preferred cyanide salts are alkali metal cyanide salts like forexample sodium cyanide or potassium cyanide.

[0217] Preferred aqueous solvents are for example aqueous dimethylsulfoxide, aqueous sulfolane, aqueous dimethyl formamide, aqueoustetrahydrofurane or aqueous dioxane. Aqueous sulfolane is especiallypreferred.

[0218] The cyanide salt is preferably used in at least an equal molaramount in respect to the compound of the formula VlI. Preferably, themolar ratio between the cyanide salt and the compound of the formula VIIis 20:1 to 1:1; especially 10:1 to 1:1, for example 8:1 to 1:1.

[0219] Preference is given to the process for the preparation ofcompounds of formula V wherein R₅₀ is —OR₅₁, —SR₅₂,

[0220] R₅₁ is C₁-C₁₂alkyl; C₂-C₁₂alkyl interrupted by oxygen; benzyl,C₅-C₈cycloalkyl or phenyl,

[0221] R₅₂ is C₁-C₁₂alkyl; C₂-C₁₂alkyl interrupted by oxygen; benzyl,C₅-C₈cycloalkyl or phenyl,

[0222] R₅₃ and R₅₄ are each independently of the other hydrogen,C₁-C₁₂alkyl; C₂-C₁₂alkyl interrupted by oxygen; benzyl, C₅-C₈cycloalkyl,or a dendrimeric or oligomeric or polymeric C₄-C₅₀hydrocarbon radical,

[0223] R₅₅ is C₁-C₁₂alkyl; C₂-C₁₂alkyl interrupted by oxygen; benzyl,C₅-C₈cycloalkyl, phenyl or a radical of formula IX

[0224] wherein R₁, R₂, R₃, R″₄, R₅ and n are as defined above, and R₅₆is C₂-C₈alkylene.

[0225] Special preference is given to the process for the preparation ofcompounds of formula V wherein R₅₀ is

[0226] R₅₃ and R₅₄ are each independently of the other hydrogen,C₁-C₁₂alkyl, benzyl, cyclohexyl or a dendrimeric C₄-C₃₀hydrocarbonradical,

[0227] R₅₅ is C₁-C₁₂alkyl, benzyl, cyclohexyl, phenyl or a radical offormula IX

[0228] wherein R₁, R₂, R₃, R″₄, R₅ and n are as defined above, and

[0229] R₅₆ is C₄-C₈alkylene.

[0230] Of special interest is the process for the preparation ofcompounds of formula V wherein

[0231] R₅₀ is

[0232] R₅₃ and R₅₄ are each independently of the other C₁-C₁₂alkyl,benzyl or a dendrimeric C₄-C₃₀hydrocarbon radical, and

[0233] R₅₆ is C₄-C₆alkylene.

[0234] The compounds of formula VII are known or can be obtained bymethods known per se, such as those disclosed in Examples 1 a, 2 a and 3a of WO-A-99/67232.

[0235] The compounds of formula I can also be prepared in a so-calledone-pot process, starting from the compounds of formula VII. In thatprocess, the compounds of formula V are prepared in situ and, withoutbeing isolated, are hydrolyzed further in an aqueous solvent in thepresence of an acid.

[0236] The present invention therefore relates also to a process for thepreparation of compounds of formula I

[0237] wherein the general symbols are as defined above, which processcomprises converting a compound of formula VII

[0238] wherein the general symbols are as defined above, with an aqueouscyanide salt solution to form a compound of formula V

[0239] wherein the general symbols are as defined above, and then,without its being isolated, hydrolyzing the compound of formula V in anaqueous solvent in the presence of an acid.

[0240] The definitions of the general symbols for the one-pot processaccording to the invention are the same as for the other process of theinvention discussed hereinbefore.

[0241] The preferred reaction parameters for the one-pot processcorrespond to the preferences for the two separate steps, which havealready been discussed in detail.

[0242] The invention relates also to novel compounds of formula V

[0243] wherein, when n is 1,

[0244] R₁is naphthyl, phenanthryl, anthryl,5,6,7,8-tetrahydro-2-naphthyl, thienyl, benzo[b]thienyl,naphtho[2,3-b]thienyl, thianthrenyl, furyl, benzofuryl, isobenzofuryl,dibenzofuryl, xanthenyl, phenoxathimnyl, pyrrolyl, imidazolyl,pyrazolyl, pyrazinyl, pyridyl, pyrimidinyl, pyridazinyl, indolizinyl,isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl,quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl,cinnolinyl, pteridinyl, carbazolyl, β-carbolinyl, phenanthridinyl,acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl,phenothiazinyl, isoxazolyl, furazanyl, biphenyl, terphenyl, fluorenyl orphenoxazinyl, each of which is unsubstituted or substituted by fluorine,hydroxy, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, C₁-C₁₈alkylthio,di(C₁-C₄alkyl)amino, phenyl, benzyl, benzoyl or by benzoyloxy or R₁ is aradical of formula II or III

[0245] when n is 2,

[0246] R₁ is phenylene or naphthylene each unsubstituted or substitutedby C₁-C₄alkyl or by fluorine; or is —R₆—X—R₇—,

[0247] R₂, R₃, R′₄ and R₅ are each independently of the others hydrogen,fluorine, hydroxy, C₁-C₂₅-alkyl, C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substituted phenyl, unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; C₁-Cl₈alkoxy, C₁-C₁₈alkylthio, C₁-C₄alkylamino,di(C₁-C₄alkyl)amino, C₁-C₂₅alkanoyloxy, C₁-C₂₅alkanoylamino;C₃-C₂₅alkanoyloxy interrupted by oxygen, sulfur or by

[0248] C₆-C₉cycloalkylcarbonyloxy, benzoyloxy or C₁-C₁₂alkyl-substitutedbenzoyloxy, or furthermore the radicals R₂ and R₃ or the radicals R₃ andR′₄ or the radicals R′₄ and R₅, together with the carbon atoms to whichthey are bonded, form a benzo ring, R′₄ is additionally —(CH₂)_(p)—COR₉or —(CH₂)_(q)OH or, when R₃ and R₅ are hydrogen, R′₄ is additionally aradical of formula VI

[0249] wherein R₁ is as defined above for the case where n=1,

[0250] R₆ and R₇ are each independently of the other phenylene ornaphthylene each unsubstituted or substituted by C₁-C₄alkyl,

[0251] R₈ is C₁-C₈alkyl,

[0252] R₉ is hydroxy,$\left\lbrack {{—O}^{-}\frac{1}{r}M^{r +}} \right\rbrack,$

[0253] C₁-C₁₈alkoxy or

[0254] R₁₀ and R₁₁ are each independently of the other hydrogen, CF₃,C₁-C₁₂alkyl or phenyl, or R₁₀ and R₁₁, together with the carbon atom towhich they are bonded, form a C₅-C₈cycloalkyl-idene ring unsubstitutedor substituted by from 1 to 3 C₁-C₄alkyl groups;

[0255] R₁₂ and R₁₃ are each independently of the other hydrogen orC₁-C₁₈alkyl,

[0256] R₁₄ is hydrogen or C₁-C₁₈alkyl,

[0257] R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ are each independently of the othershydrogen, halogen, fluoro-substituted C₁-C₁₂alkyl; —CN,

[0258] —SO₂R₄₆, SO₃R₄₆, hydroxy, C₁-C₂₅alkyl; C₂-C₂₅alkyl interrupted byoxygen, sulfur or by

[0259] C₁-C₂₅alkoxy; C₂-C₂₅alkoxy interrupted by oxygen, sulfur or by

[0260] C₁-C₂₅alkylthio, C₇-C₉phenylalkyl, C₇-C₉phenylalkoxy,unsubstituted or C₁-C₄alkyl-substituted phenyl; unsubstituted orC₁-C₄alkyl-substituted phenoxy; unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkoxy; di(C₁-C₄alkyl)amino, C₁-C₂₅alkanoyl; C₃-C₂₅alkanoylinterrupted by oxygen, sulfur or by

[0261] C₁-C₂₅alkanoyloxy; C₃- C₂₅alkanoyloxy interrupted by oxygen,sulfur or by

[0262] C₁-C₂₅alkanoylamino, C₆-C₉cycloalkylcarbonyl,C₆-C₉cycloalkylcarbonyloxy, benzoyl or C₁-C₁₂alkyl-substituted benzoyl;benzoyloxy or C₁-C₁₂alkyl-substituted benzoyloxy;

[0263] R₂₄ is hydrogen, C₁-C₄alkyl, or unsubstituted orC₁-C₄alkyl-substituted phenyl,

[0264] R₂₅ and R₂₆ are hydrogen, C₁-C₄alkyl or phenyl, with the provisothat at least one of the radicals R₂₅ and R₂₆ is hydrogen,

[0265] R₂₇ and R₂₈ are each independently of the other hydrogen,C₁-C₄alkyl or phenyl,

[0266] R₂₉ is hydrogen or C₁-C₄alkyl,

[0267] R₃₀ is hydrogen, unsubstituted or C₁-C₄alkyl-substituted phenyl;C₁-C₂₅alkyl; C₂-C₂₅alkyl interrupted by oxygen, sulfur or by

[0268] C₇-C₉phenylalkyl unsubstituted or substituted on the phenylradical by from 1 to 3 C₁-C₄alkyl groups; or C₇-C₂₅phenylalkylinterrupted by oxygen, sulfur or by

[0269] and unsubstituted or substituted on the phenyl radical by from 1to 3 C₁-C₄alkyl groups,

[0270] R₃₁ is hydrogen or C₁-C₄alkyl,

[0271] R₃₂ is hydrogen, C₁-C₂₅alkanoyl; C₃-C₂₅alkanoyl interrupted byoxygen, sulfur or by

[0272] C₂-C₂₅alkanoyl substituted by a di(C₁-C₆alkyl) phosphonate group;C₆-C₉cyclo-alkylcarbonyl, thenoyl, furoyl, benzoyl, orC₁-C₁₂alkyl-substituted benzoyl;

[0273] R₃₃ is hydrogen or C₁-C₈alkyl,

[0274] R₃₄ is a direct bond, C₁-C₁₈alkylene; C₂-C₁₈alkylene interruptedby oxygen, sulfur or by

[0275] C₂-C₂₀alkylidene, C₇-C₂₀phenylalkylidene, C₅-C₈cycloalkylene,C₇-C₈bicycloalkylene, unsubstituted or C₁-C₄alkyl-substituted phenylene,

[0276] R₃₅ is hydroxy,$\left\lbrack {{—O}^{-}\frac{1}{r}M^{r +}} \right\rbrack,$

[0277] C₁-C₁₈alkoxy or$\left\lbrack {{—O}^{-}\frac{1}{r}M^{r +}} \right\rbrack,$

[0278] R₃₆ is oxygen, —NH— or

[0279] R₃₇ is C₁-C₁₈alkyl or phenyl,

[0280] R₄₂ is hydrogen, hydroxy,$\left\lbrack {{—O}^{-}\frac{1}{r}M^{r +}} \right\rbrack,$

[0281] C₁-C₂₅alkyl, C₇-C₉phenylalkyl, unsubstituted orC₁-C₄alkyl-substituted phenyl; unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; or C₃-C₂₅alkyl which is interrupted by oxygen, sulfuror $\left\lbrack {{—O}^{-}\frac{1}{r}M^{r +}} \right\rbrack,$

[0282] R₄₃ is C₁-C₂₅alkyl, C₇-C₉phenylalkyl, unsubstituted orC₁-C₄alkyl-substituted phenyl; unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; or C₃-C₂₅alkyl which is interrupted by oxygen, sulfuror

[0283] R₄₄ and R₄₅ are each independently of one another hydrogen,C₁-C₂₅alkyl, hydroxyl-substituted C₂-C₂₄alkyl; C₃-C₂₅alkyl which isinterrupted by oxygen, sulfur or

[0284] phenylalkyl which is unsubstituted or is substituted on thephenyl ring by C₁-C₄alkyl; or C₃-C₂₄alkenyl; or R₄₄ and R₄₅, togetherwith the nitrogen atom to which they are attached, form a 5-, 6- or7-membered heterocyclic ring which is unsubstituted or is substituted byC₁-C₄alkyl or is interrupted by oxygen, sulfur or

[0285] R₄₆ is hydrogen or C₁-C₂₅alkyl,

[0286] M is an r-valent metal cation,

[0287] X is a direct bond, oxygen, sulfur or —NR₁₄—,

[0288] n is 1 or 2,

[0289] p is 0, 1 or2,

[0290] q is 1,2,3,4,5 or6,

[0291] r is 1, 2 or 3, and

[0292] S is 0, 1 or 2; with the proviso that, when R₂, R₃, R₅, R₁₉, R₂₀,R₂₁, R₂₂ and R₂₃ are hydrogen,

[0293] R′₄ is not methylthio.

[0294] The preferred general symbols for the novel compounds of formulaV correspond to those in the preferred general symbols set outhereinbefore for the process according to the invention for thepreparation of compounds of formula I.

[0295] The compounds of the formula I are suitable for stabilizingorganic materials against oxidative, thermal or light-induceddegradation. Special attention is drawn to their excellent action asantioxidants in the stabilization of organic materials.

[0296] Illustrative examples of such materials are:

[0297] 1. Polymers of monoolefins and diolefins, for examplepolypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyisoprene or polybutadiene, as well as polymers of cycloolefins, forinstance of cyclopentene or norbornene, polyethylene (which optionallycan be crosslinked), for example high density polyethylene (HDPE), highdensity and high molecular weight polyethylene (HDPE-HMW), high densityand ultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), (VLDPE) and (ULDPE).

[0298] Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

[0299] a) radical polymerisation (normally under high pressure and atelevated temperature). b) catalytic polymerisation using a catalyst thatnormally contains one or more than one metal of groups IVb, Vb, VIb orVIII of the Periodic Table. These metals usually have one or more thanone ligand, typically oxides, halides, alcoholates, esters, ethers,amines, alkyls, alkenyls and/or aryls that may be either π- orσ-coordinated. These metal complexes may be in the free form or fixed onsubstrates, typically on activated magnesium chloride, titanium(III)chloride, alumina or silicon oxide. These catalysts may be soluble orinsoluble in the polymerisation medium. The catalysts can be used bythemselves in the polymerisation or further activators may be used,typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyloxides or metal alkyloxanes, said metals being elements of groups Ia,IIa and/or IIIa of the Periodic Table. The activators may be modifiedconveniently with further ester, ether, amine or silyl ether groups.These catalyst systems are usually termed Phillips, Standard OilIndiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single sitecatalysts (SSC).

[0300] 2. Mixtures of the polymers mentioned under 1), for examplemixtures of polypropylene with polyisobutylene, polypropylene withpolyethylene (for example PP/HDPE, PP/LDPE) and mixtures of differenttypes of polyethylene (for example LDPE/HDPE).

[0301] 3. Copolymers of monoolefins and diolefins with each other orwith other vinyl monomers, for example ethylene/propylene copolymers,linear low density polyethylene (LLDPE) and mixtures thereof with lowdensity polyethylene (LDPE), propylene/but-l-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

[0302] 4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

[0303] 5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

[0304] 6. Copolymers of styrene or o-methylstyrene with dienes oracrylic derivatives, for example styrene/butadiene,styrene/acrylonitrile, styrene/alkyl methacrylate,styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate,styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate;mixtures of high impact strength of styrene copolymers and anotherpolymer, for example a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer; and block copolymers of styrenesuch as styrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

[0305] 7. Graft copolymers of styrene or a-methylstyrene, for examplestyrene on polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

[0306] 8. Halogen-containing polymers such as polychloroprene,chlorinated rubbers, chlorinated and brominated copolymer ofisobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinatedpolyethylene, copolymers of ethylene and chlorinated ethylene,epichlorohydrin homo- and copolymers, especially polymers ofhalogen-containing vinyl compounds, for example polyvinyl chloride,polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, aswell as copolymers thereof such as vinyl chloride/vinylidene chloride,vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetatecopolymers.

[0307] 9. Polymers derived from α,β-unsaturated acids and derivativesthereof such as polyacrylates and polymethacrylates; polymethylmethacrylates, polyacrylamides and polyacrylonitriles, impact-modifiedwith butyl acrylate.

[0308] 10. Copolymers of the monomers mentioned under 9) with each otheror with other unsaturated monomers, for example acrylonitrile/ butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

[0309] 11. Polymers derived from unsaturated alcohols and amines or theacyl derivatives or acetals thereof, for example polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine;as well as their copolymers with olefins mentioned in 1) above.

[0310] 12. Homopolymers and copolymers of cyclic ethers such aspolyalkylene glycols, polyethylene oxide, polypropylene oxide orcopolymers thereof with bisglycidyl ethers.

[0311] 13. Polyacetals such as polyoxymethylene and thosepolyoxymethylenes which contain ethylene oxide as a comonomer;polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

[0312] 14. Polyphenylene oxides and sulfides, and mixtures ofpolyphenylene oxides with styrene polymers or polyamides.

[0313] 15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

[0314] 16. Polyamides and copolyamides derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, for example polyamide 4, polyamide 6, polyamide6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromaticpolyamides starting from m-xylene diamine and adipic acid; polyamidesprepared from hexamethylenediamine and isophthalic or/and terephthalicacid and with or without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

[0315] 17. Polyureas, polyimides, polyamide-imides, polyetherimids,polyesterimids, polyhydantoins and polybenzimidazoles.

[0316] 18. Polyesters derived from dicarboxylic acids and diols and/orfrom hydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate(PAN) and polyhydroxybenzoates, as well as block copolyether estersderived from hydroxyl-terminated polyethers; and also polyestersmodified with polycarbonates or MBS.

[0317] 19. Polycarbonates and polyester carbonates.

[0318] 20. Polysulfones, polyether sulfones and polyether ketones.

[0319] 21. Crosslinked polymers derived from aldehydes on the one handand phenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

[0320] 22. Drying and non-drying alkyd resins.

[0321] 23. Unsaturated polyester resins derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

[0322] 24. Crosslinkable acrylic resins derived from substitutedacrylates, for example epoxy acrylates, urethane acrylates or polyesteracrylates.

[0323] 25. Alkyd resins, polyester resins and acrylate resinscrosslinked with melamine resins, urea resins, isocyanates,isocyanurates, polyisocyanates or epoxy resins.

[0324] 26. Crosslinked epoxy resins derived from aliphatic,cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g.products of diglycidyl ethers of bisphenol A and bisphenol F, which arecrosslinked with customary hardeners such as anhydrides or amines, withor without accelerators.

[0325] 27. Natural polymers such as cellulose, rubber, gelatin andchemically modified homologous derivatives thereof, for examplecellulose acetates, cellulose propionates and cellulose butyrates, orthe cellulose ethers such as methyl cellulose; as well as rosins andtheir derivatives.

[0326] 28. Blends of the aforementioned polymers (polyblends), forexample PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS,PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates,POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS,PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABSor PBT/PET/PC.

[0327] 29. Naturally occurring and synthetic organic materials which arepure monomeric compounds or mixtures of such compounds, for examplemineral oils, animal and vegetable fats, oil and waxes, or oils, fatsand waxes based on synthetic esters (e.g. phthalates, adipates,phosphates or trimellitates) and also mixtures of synthetic esters withmineral oils in any weight ratios, typically those used as spinningcompositions, as well as aqueous emulsions of such materials.

[0328] 30. Aqueous emulsions of natural or synthetic rubber, e.g.natural latex or latices of carboxylated styrene/butadiene copolymers.

[0329] Further objects of the invention are therefore compositionscomprising a) an organic material which is susceptible to oxidative,thermal or light-induced degradation, and b) at least one compound ofthe formula V.

[0330] Preferred organic materials are natural, semi-synthetic or,preferably, synthetic polymers.

[0331] Particularly referred organic materials are synthetic polymers,most preferably thermoplastic polymers. Especially preferred organicmaterials are polyacetals, polyolefins such as polypropylene orpolyethylene, polyether/polyurethanes, polyesters such as polybutyleneterephthalate, polycarbonates or vulcanisates.

[0332] To be singled out for special mention is the efficacy of thenovel compounds of the formula I against oxidative or thermaldegradation, especially under the action of heat which occurs during theprocessing of thermoplasts. The compounds of the formula I of thisinvention are therefore admirably suited for use as processingstabilizers.

[0333] The compounds of the formula I will preferably be added to theorganic material to be stabilized in concentrations of 0.0005 to 10%,preferably 0.001 to 2%, typically 0.01 to 2%, based on the weight ofsaid material.

[0334] In addition to comprising the compounds of the formula I, theinventive compositions may comprise further co-stabilizers, typicallythe following:

[0335] 1. Antioxidants

[0336] 1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(a-methylcyclohexyl)-4,6-dimethyl-phenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example 2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

[0337] 1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctyl-thiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

[0338] 1.3. Hydroguinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

[0339] 1.4. Tocopherols, for example α-tocopherol, β-tocopherol,γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

[0340] 1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.

[0341] 1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butyl-phenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

[0342] 1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxy-benzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

[0343] 1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,didodecylmercaptoethyi-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

[0344] 1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

[0345] 1.10. Triazine compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

[0346] 1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

[0347] 1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

[0348] 1.13. Esters of D-(3,5-di-tert-butyl-4-hydroxyphenyl)propionicacid with mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0349] 1.14. Esters ofβ-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- orpoly-hydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;3,9-bis[2-{3-(3-tertbutyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.

[0350] 1.15. Esters of β-(3,5-dicyclohexal-4-hydroxyphenyl)propionicacid with mono- or polyhydric alcohols, e.g. with methanol, ethanol,octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0351] 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0352] 1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionicacid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide.N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugarde®XL-1, supplied by Uniroyal).

[0353] 1.18. Ascorbic acid (vitamin C)

[0354] 1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-disec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenyl-amine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyidiphenylamine, 4-n-butyl-aminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyidiphenylamines, a mixture of mono- anddialkylated nonyidiphenylamines, a mixture of mono- and dialkylateddodecyidiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert-butyidiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylatedtertbutyl/tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octylphenothiazines, N-allylphenothiazine,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetra-methylpiperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

[0355] 2. UV absorbers and light stabilizers

[0356] 2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)benzo-triazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-ditert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis(as,-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyl-oxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonyl-ethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxy-phenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol

[0357] 300; [R—CH₂CH₂—COO—CH₂CH₂]₂, whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,2-[2′-hydroxy-3′-(1,1,3,3-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazole;2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)phenyl]benzotriazole.

[0358] 2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy,4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy derivatives.

[0359] 2.3. Esters of substituted and unsubstituted benzoic acids, forexample 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

[0360] 2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate,isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate,methyl α-cyano-β-methyl-p-methoxycinnamate, butylα-cyano-β-methyl-p-methoxycinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

[0361] 2.5. Nickel compounds, for example nickel complexes of2,2′-thiobis[4-(1,1,3,3-tetramethyl-butyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

[0362] 2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)-malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)-ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); a condensate of 1,6-hexanediamine and2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268-64-7]);N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decaneand epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,a diester of 4-methoxymethylenemalonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, areaction product of maleic acid anhydride-α-olefin copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.

[0363] 2.7. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

[0364] 2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyhenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

[0365] 3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

[0366] 4. Phosphites and phosphonites, for example triphenyl phosphite,diphenylalkyl phosphites, phenyidialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,4-dicumylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,2,2′,2″-nitrilo-[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite,5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.

[0367] 5. Hydroxylamines, for example N, N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

[0368] 6. Nitrones, for example N-benzyl-alpha-phenyinitrone,N-ethyl-alpha-methyinitrone, N-octyl-alpha-heptyinitrone,N-lauryl-alpha-undecyinitrone, N-tetradecyl-alpha-tridecylnitrone,N-hexadecyl-alpha-pentadecylnitrone,N-octadecyl-alpha-heptadecylnitrone,N-hexadecyl-alpha-heptadecylnitrone,N-ocatadecyl-alpha-pentadecylnitrone,N-heptadecyl-alpha-hepta-decylnitrone,N-octadecyl-alpha-hexadecyinitrone, nitrone derived fromN,N-dialkylhydroxyl-amine derived from hydrogenated tallow amine.

[0369] 7. Thiosynergists, for example dilauryl thiodipropionate ordistearyl thiodipropionate.

[0370] 8. Peroxide scavengers, for example esters of β-thiodipropionicacid, for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

[0371] 9. Polyamide stabilizers, for example copper salts in combinationwith iodides and/or phosphorus compounds and salts of divalentmanganese.

[0372] 10. Basic co-stabilizers, for example melamine,polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, ureaderivatives, hydrazine derivatives, amines, polyamides, polyurethanes,alkali metal salts and alkaline earth metal salts of higher fatty acids,for example calcium stearate, zinc stearate, magnesium behenate,magnesium stearate, sodium ricinoleate and potassium palmitate, antimonypyrocatecholate or zinc pyrocatecholate.

[0373] 11. Nucleating agents, for example inorganic substances, such astalcum, metal oxides, such as titanium dioxide or magnesium oxide,phosphates, carbonates or sulfates of, preferably, alkaline earthmetals; organic compounds, such as mono- or polycarboxylic acids and thesalts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid,diphenylacetic acid, sodium succinate or sodium benzoate; polymericcompounds, such as ionic copolymers (ionomers). Especially preferred are1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol,1,3:2,4-di(paramethyldibenzylidene)sorbitol, and1,3:2,4-di(benzylidene)sorbitol.

[0374] 12. Fillers and reinforcing agents, for example calciumcarbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin,mica, barium sulfate, metal oxides and hydroxides, carbon black,graphite, wood flour and flours or fibers of other natural products,synthetic fibers.

[0375] 13. Other additives, for example plasticisers, lubricants,emulsifiers, pigments, rheology additives, catalysts, flow-controlagents, optical brighteners, flameproofing agents, antistatic agents andblowing agents.

[0376] 14. Benzofuranones and indolinones, for example those disclosedin U.S. Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No.5,175,312; U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643;DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102or 3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butylbenzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]-benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxylphenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one.

[0377] The co-stabilizers are typically used in concentrations of 0.01to 10%, based on the total weight of the material to be stabilized.

[0378] The novel compounds of the formula V can be used in particulartogether with phenolic antioxidants, light stabilizers and/or processingstabilizers.

[0379] Other preferred compositions comprise, in addition to compoundsof the formula I, a compound of the organic phosphite or phosphonitetype.

[0380] The fillers and reinforcing agents (point 12 of the list), suchas, for example, talc, calcium carbonate, mica or kaolin, are added tothe polyolefins, for example, in concentrations of from 0.01 to 40%,based on the total weight of the polyolefins to be stabilized.

[0381] The fillers and reinforcing agents (point 12 of the list), suchas, for example, metal hydroxides, especially aluminium hydroxide ormagnesium hydroxide, are added to the polyolefins, for example, inconcentrations of from 0.01 to 60%, based on the total weight of thepolyolefins to be stabilized.

[0382] Carbon black, as filler, is added to the polyolefinsadvantageously in concentrations of from 0.01 to 5%, based on the totalweight of the polyolefins to be stabilized.

[0383] Glass fibres, as reinforcing agents, are added to the polyolefinsadvantageously in concentrations of from 0.01 to 20%, based on the totalweight of the polyolefins to be stabilized.

[0384] Also of interest as yet further additives in the compositionsaccording to the invention are alkaline earth metal salts of higherfatty acids, such as, for example, calcium stearate; calcium lactateand/or calcium stearoyl-2-lactylate.

[0385] As a conventional stabilizer combination for the processing ofpolymeric organic materials, such as, for example, polyolefins, intocorresponding moulded articles, the combination of a phenolicantioxidant with a secondary antioxidant based on an organic phosphiteor phosphonite is recommended. Depending on the substrate and process,however, many polyolefin processors are obliged to operate processes inthe high-temperature range above approx. 280° C. The inclusion of aprocessing stabilizer of the formula V is particularly suitable forhigh-temperature applications, especially in the temperature range above300° C. Technical materials and moulded articles for instance based onHD polyethylene, such as, for example, pipes and their technicalvariants (fittings), can be manufactured with a higher output and fewerrejects. A further advantage of the compounds of the formula V is alsothat they can be used in a very small amount, which results in areduction in the overall antioxidant concentration compared withconventional stabilizer mixtures. For instance the use of a lowconcentration of a compound of the formula I allows the overallstabilizer concentration to be reduced by approximately a third in, forexample, polyolefins, which at the same time represents an economicadvantage.

[0386] The compounds of the formula V and other optional additives areincorporated into the organic polymeric material according to knownmethods, for example before or during shaping to moulded articles oralternatively by coating the organic polymeric material with a solutionor dispersion of the compounds and subsequently evaporating the solvent.The compounds of the formual V can also be added to the materials to bestabilized in the form of a master batch which contains these compounds,typically in a concentration of, for example, from 2.5 to 25% by weight.

[0387] The compounds of the formula V may also be added before or duringpolymerization or before crosslinking.

[0388] In this connection, particular attention is drawn to thesurprising feature that the novel compounds of the formula V inhibitdiscoloration, especially so-called pinking in the manufacture of e.g.polyurethane foams.

[0389] The compounds of the formula V, and where applicable furtheradditives, may be incorporated into the material to be stabilized inpure form or encapsulated in waxes, oils or polymers.

[0390] The compounds of the formula V, and where applicable furtheradditives, may also be sprayed onto the polymer to be stabilized. Theyare able to be used to dilute other additives (e.g. the above-mentionedconventional additives) or melts thereof, so that they can also besprayed together with these additives onto the polymer to be stabilized.Application by spraying during the deactivation of the polymerizationcatalysts is especially advantageous, in which case spraying isconveniently effected with the vapour used for deactivation.

[0391] The materials stabilized in that manner may be used in anextremely wide variety of forms, e.g. in the form of films, fibres,tapes, moulding compounds or profiles, or as binders forsurface-coatings, especially powder coatings, adhesives or cements.

[0392] The polyolefins stabilized in that manner may likewise be used inan extremely wide variety of forms, especially in the form ofthick-layer polyolefin moulded articles that are in lasting contact withextracting media, such as, for example, pipes for liquids or gases,films, fibres, geomembranes, tapes, profiles or tanks.

[0393] The preferred thick-layer polyolefin moulded articles have alayer thickness of from 1 to 50 mm, especially from 1 to 30 mm, e.g.from 2 to 10 mm.

[0394] A preferred embodiment of this invention is therefore the use ofcompounds of the formula V as stabilizers for organic materials againstoxidative, thermal or light-induced degradation.

[0395] The invention also relates to a process for stabilizing anorganic material against oxidative, thermal or light-induceddegradation, which comprises incorporating therein or applying theretoat least one compound of the formula V.

[0396] The invention relates also to compositions comprising afunctional fluid, preferably from the series of lubricants, hydraulicfluids and metal-working fluids and also fuels for powering engines ofthe 4-stroke, Otto, 2-stroke, diesel, Wankel and orbital types, and atleast one compound of the formula V.

[0397] The compounds of the formula V may preferably be used inlubricants and fuels as multifunctional stabilizers, that is to say theycombine in themselves antioxidative, friction-reducing.extreme-pressure-protection and wear-protection action and alsoanti-corrosion properties.

[0398] Preferred lubricants and fuels and related products are engineoils, turbine oils, gear oils, hydraulic fluids, diesel or Otto fuels,metal-working fluids and lubricating greases.

[0399] Especially preferred lubricants are mineral oils, synthetic oilsor mixtures thereof.

[0400] Products known per se are used as functional fluids from theseries of lubricants, hydraulic fluids and metal-working fluids.

[0401] The lubricants and hydraulic fluids that come into considerationwill be familiar to the person skilled in the art and are described inthe relevant specialist literature, such as, for example, in DieterKlamann, “Schmierstoffe und verwandte Produkte” [Lubricants and relatedproducts] (Verlag Chemie, Weinheim, 1982), in Schewe-Kobek, “DasSchmiermittel-Taschenbuch” [The lubricant handbook] (Dr. AlfredHuthig-Verlag, Heidelberg, 1974) and in “Ullmanns Enzyklopa die dertechnischen Chemie” [Ullmann's Encyclopaedia of Industrial Chemistry],Vol. 13, pages 85-94 (Verlag Chemie, Weinheim, 1977).

[0402] The lubricants are especially oils and greases, for example basedon a mineral oil. Oils are preferred.

[0403] A further group of lubricants that may be used are vegetable oranimal oils, greases, tallows and waxes or mixtures thereof with oneanother or mixtures with the mentioned mineral or synthetic oils.

[0404] Vegetable and animal oils, greases, tallows and waxes are, forexample, palm-kernel oil, palm oil, olive oil, rapeseed oil, rape oil,linseed oil, groundnut oil, soybean oil, cottonseed oil, sunflower oil,pumpkin seed oil, coconut oil, maize oil, castor oil, tree nut oil andmixtures thereof, fish oils, tallows obtained from slaughtered animals,such as beef tallow, neatsfoot oil and bone oil, and modified,epoxidised and sulfoxidised forms thereof, for example epoxidisedsoybean oil.

[0405] The mineral oils are based especially on hydrocarbon compounds.

[0406] Examples of synthetic lubricants include lubricants based onaliphatic or aromatic carboxy esters, polymeric esters, polyalkyleneoxides, phosphoric acid esters, poly-alpha-olefins or silicones, adiester of a divalent acid with a monohydric alcohol, such as, forexample, dioctyl sebacate or dinonyl adipate, a triester oftrimethylolpropane with a monovalent acid or with a mixture of suchacids, such as, for example, trimethylolpropane tripelargonate,trimethylolpropane tricaprylate or mixtures thereof, a tetraester ofpentaerythritol with a monovalent acid or with a mixture of such acids,such as, for example, pentaerythritol tetracaprylate, or a complex esterof monovalent and divalent acids with polyhydric alcohols, for example acomplex ester of trimethylolpropane with caprylic and sebacic acid, or amixture thereof. Apart from mineral oils there are especially suitable,for example, poly-alpha-olefins, ester-based lubricants, phosphates,glycols, polyglycols and polyalkylene glycols, and also mixtures thereofwith water.

[0407] Metal-working fluids and hydraulic fluids may be prepared on thebasis of the same substances as those described above for thelubricants, such fluids frequently being emulsions of such substances inwater or other liquids.

[0408] Lubricant and fuel compositions according to the invention areused, for example, in internal combustion engines, e.g. in motorisedvehicles equipped with, for example, engines of the Otto, diesel,two-stroke, Wankel or orbital type.

[0409] The compounds of the formula V are readily soluble in lubricantsand fuels, metal-working fluids and hydraulic fluids and are thereforeespecially suitable as additives for lubricants and fuels, metal-workingfluids and hydraulic fluids.

[0410] As additives in lubricants, the compounds of the formula V areeffective even in very small amounts. They are mixed in with thelubricants advantageously in an amount of from 0.01 to 5% by weight,preferably in an amount of from 0.05 to 3% by weight and very especiallyin an amount of from 0.1 to 2% by weight, in each case based on thelubricant.

[0411] The compounds of the formula V may be mixed in with thelubricants and fuels in a manner known per se. The compounds of theformula V are readily soluble, for example, in oils. It is also possibleto prepare a so-called master batch, which may be diluted, as a functionof use, with the appropriate lubricant or fuel to the concentrationssuitable for use. In such cases concentrations above 1% by weight arepossible.

[0412] The lubricants and fuels, metal-working fluids and hydraulicfluids may additionally comprise other additives that are added in orderto improve their basic properties still further; such additives include:further antioxidants, metal passivators, rust inhibitors, viscosityindex improvers, pour-point depressants, dispersants, detergents,coefficient of friction reducers, further extreme-pressure additives andanti-wear additives. Such further additives are added advantageously inan amount of from 0.01 to 5% by weight.

[0413] A number of such compounds can be found, for example, in theabove list “1. Antioxidants”, especially points 1.1 to 1.19. Inaddition, further additives may be mentioned by way of example:

[0414] Examples of further antioxidants:

[0415] Aliphatic or aromatic phosphites, esters of thiodipropionic acidor thiodiacetic acid or salts of dithiocarbamic or dithiophosphoricacid, 2,2,12,12-tetramethyl-5,9-dihydroxy-3,7,11 -trithiatridecane and2,2,15,15-tetramethyl-5,12-dihydroxy-3,7,10,14-tetrathiahexadecane.

[0416] Examples of metal deactivators. e.g. for copper, are:

[0417] a) Benzotriazoles and derivatives thereof, e.g.2-mercaptobenzotriazole, 2,5-dimercaptobenzotriazole, 4- or5-alkylbenzotriazoles (e.g. tolutriazole) and derivatives thereof,4,5,6,7-tetrahydrobenzotriazole, 5,5′-methylenebis-benzotriazole;Mannich bases of benzotriazole or tolutriazole, such as1-[di(2-ethylhexyl)aminomethyl]tolutriazole and1-[di(2-ethylhexyl)aminomethyl]benzotriazole; alkoxyalkylbenzotriazoles,such as 1-(nonyloxymethyl)benzotriazole, 1-(1-butoxyethyl)benzotriazoleand 1-(1-cyclohexyloxybutyl)-tolutriazole.

[0418] b) 1,2,4-Triazoles and derivatives thereof, e.g. 3-alkyl- (or-aryl-)1,2,4-triazoles, Mannich bases of 1,2,4-triazoles, such as1-[di(2-ethylhexyl)aminomethyl]-1,2,4-triazole;alkoxyalkyl-1,2,4-triazoles, such as 1-(1-butoxyethyl)-1,2,4-triazole;acylated 3-amino-1,2,4-triazoles.

[0419] c) Imidazole derivatives, e.g.4,4′-methylenebis(2-undecyl-5-methyl)imidazole andbis[(N-methyl)imidazol-2-yl]carbinol-octyl ether.

[0420] d) Sulfur-containing heterocyclic compounds, e.g.2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole,2,5-dimercaptobenzothiadiazole and derivatives thereof;3,5-bis[di(2-ethylhexyl)aminomethyl]-1,3,4-thiadiazolin-2-one.

[0421] e) Amino compounds, e.g. salicylidene-propylenediamine,salicylaminoguanidine and salts thereof.

[0422] Examples of rust inhibitors are:

[0423] a) Organic acids, their esters, metal salts, amine salts andanhydrides, e.g. alkyl- and alkenyl-succinic acids and their partialesters with alcohols, diols or hydroxycarboxylic acids, partial amidesof alkyl- and alkenyl-succinic acids, 4-nonylphenoxyacetic acid, alkoxy-and alkoxyethoxy-carboxylic acids, such as dodecyloxyacetic acid,dodecyloxy-(ethoxy)acetic acid and amine salts thereof, and alsoN-oleoyl-sarcosine, sorbitan monooleate, lead naphthenate,alkenylsuccinic acid anhydrides, e.g. dodecenylsuccinic acid anhydride,2-(2-carboxyethyl)-1-dodecyl-3-methylglycerol and salts thereof,especially sodium and triethanolamine salts thereof.

[0424] b) Nitrogen-containing compounds, e.g.:

[0425] i. Primary, secondary or tertiary, aliphatic or cycloaliphaticamines and amine salts of organic and inorganic acids, e.g. oil-solublealkylammonium carboxylates, and1-[N,N-bis(2-hydroxyethyl)amino]-3-(4-nonylphenoxy)propan-2-ol.

[0426] ii. Heterocyclic compounds, e.g.: substituted imidazolines andoxazolines, e.g. 2-hepta-decenyl-1-(2-hydroxyethyl)-imidazoline.

[0427] c) Phosphorus-containing compounds, e.g.:

[0428] Amine salts of phosphoric acid partial esters or phosphonic acidpartial esters, zinc dialkyldithiophosphates.

[0429] d) Sulfur-containing compounds, e.g.:

[0430] Barium dinonylnaphthalene sulfonates, calcium petroleumsulfonates, alkylthio-substituted aliphatic carboxylic acids, esters ofaliphatic 2-sulfocarboxylic acids and salts thereof.

[0431] e) Glycerol derivatives, e.g.:

[0432] Glycerol monooleate,1-(alkylphenoxy)-3-(2-hydroxyethyl)glycerols,1-(alkylphenoxy)-3-(2,3-dihydroxypropyl)glycerols,2-carboxyalkyl-1,3-dialkylglycerols.

[0433] Examples of viscosity index improvers are:

[0434] Polyacrylates, polymethacrylates, vinylpyrrolidone/methacrylatecopolymers, polyvinylpyrrolidones, polybutenes, olefin copolymers,styrene/acrylate copolymers, polyethers.

[0435] Examples of pour-point depressants are:

[0436] Poly(meth)acrylates, ethylene/vinyl acetate copolymer,alkylpolystyrenes, fumarate copolymers, alkylated naphthalenederivatives.

[0437] Examples of dispersants/surfactants are:

[0438] Polybutenylsuccinic acid amides or imides, polybutenylphosphonicacid derivatives, basic magnesium, calcium and barium sulfonates andphenolates.

[0439] Examples of extreme-pressure and anti-wear additives are:

[0440] Sulfur- and/or phosphorus- and/or halogen-containing compounds,such as, for example, chlorinated paraffins, sulfurated olefins orvegetable oils (soybean/rape oil), alkyl- or aryl-di-or -tri-sulfides,zinc dialkyldithiophosphates, zinc dithiocarbamates such as zincdiamyldithiocarbamate, molybdenum dithioates such as molybdenumdithiocarbamates, triaryl phosphates such as tritolyl phosphate,tricresyl phosphate, phenyl phosphate isopropyl ester, amine salts ofmono- or di-alkylphosphoric acids such as the amine salts ofmono-/di-hexyl phosphate, amine salts of alkylphosphonic acids such asthe amine salt of methylphosphonic acid, triaryl phosphites such astrisnonylphenyl] phosphite, dialkyl phosphites such as dioctylphosphite, triaryl monothiophosphates such as triphenyl thionophosphateor tris[isononylphenyl] thionophosphate or tert-butylated triphenylthionophosphate, substituted trialkyl mono- or di-thiophosphates such asdiisopropoxyphosphinothioyl)thio]propionate orbutylene-1,3-bis[(diisobutoxyphosphinothioyl)propionate,trithiophosphates such as trithiophosphoric acidS,S,S-tris(isooctyl-2-acetates), amine salts of3-hydroxy-1,3-thiaphosphetane-3-oxide, benzotriazoles or derivativesthereof such as bis(2-ethylhexyl)aminomethyl-tolutriazole,dithiocarbamates such as methylene-bis-dibutyldithiocarbamate,derivatives of 2-mercaptobenzothiazole such as1-[N,N-bis(2-ethylhexyl)aminomethyl]-2-mercapto-1H-1,3-benzothiazole,derivatives of 2,5-dimercapto-1,3,4-thiadiazole such as2,5-bis(tert-nonyidithio)-1,3,4-thiadiazole.

[0441] Examples of coefficient of friction reducers are:

[0442] Lard oil, oleic acid, tallow, rape oil, sulfurated fats, amines.Further examples are given in EP-A-0 565 487.

[0443] Examples of special additives for use in water/oil metal-workingfluids and hydraulic fluids are:

[0444] Emulsifiers: petroleum sulfonates, amines, such aspolyoxyethylated fatty amines, non-ionic surface-active substances;

[0445] buffers: alkanolamines;

[0446] biocides: triazines, thiazolinones, tris-nitromethane,morpholine, sodium pyridenethol;

[0447] speed improvers: calcium and barium sulfonates;

[0448] Examples of fuel additives:

[0449] Fuel additives are described in Kirk-Othmer, Encyclopedia ofChemical Technology, Vol 12, 1994 and in this instance are essentiallypetrol and diesel additives:

[0450] Petrol: dyes, especially azo dyes;

[0451] Antioxidants: aminic, especially para-phenylenediamines, orphenolic, e.g. 2,6-di-tert-butyl-phenol, as described above;

[0452] Metal deactivators: especially N,N′-disalicylidene-1,2-propane,benzotriazole, EDTA;

[0453] Rust inhibitors: for example carboxylic acids, sulfonates, aminesor amine salts;

[0454] Dispersants: e.g. esters, high-molecular-weight amines, Mannichbases, succinimides, borated succinimides;

[0455] Detergents: for example fatty acid amides, nonpolymeric amines,polybutene succinimides, polyether amines, low-molecular-weight amines,sulfonates, salicylic acid derivatives;

[0456] Demulsifiers: for example long-chain alcohols or phenolscontaining poly-ethylene or -butylene groups;

[0457] Antiknock agents: tetralkyl lead, manganesemethylcyclopentadienyltricarbonyl;

[0458] Oxygen compounds: esters of vegetable oils, ethers, alcohols forimproving burn behaviour;

[0459] Diesel: ignition improvers (cetane improvers), e.g. alkylnitrates, ether nitrates, alkyl diglycol nitrates, organic peroxides;

[0460] Stabilizers for, especially, cracked diesel: amines and otherN-containing compounds that act as radical traps.

[0461] Especially preferred further additives in lubricants are aminicantioxidants, especially mixtures of mono- and di-alkylatedtert-butyl-/tert-octyl-diphenylamines.

[0462] The present invention relates also to the use of the compounds ofthe formula V for stabilizing organic materials, especially as additivesin lubricants and fuels, hydraulic fluids or metal-working fluids,preferably in hydraulic oils and gear oils. The use according to theinvention includes protection of the metal components to be lubricatedagainst mechanical attrition (wear protection) and corrosion protectionactivity and also antioxidation activity—with respect both to thelubricant and to the metal components.

[0463] The present invention accordingly relates also to a method forimproving the properties, during use, of organic materials, especiallylubricants and fuels, metal-working fluids and hydraulic fluids, whereina compound of the formula V is added to those materials.

[0464] The compounds of formula V are also suitable as scavengers forthe oxidized developer (Dox scavengers) in color photographic material.

[0465] The photographic materials according to this invention comprise asupport bearing at least one layer of a light-sensitive silver halideemulsion.

[0466] Examples of color photographic materials according to thisinvention are color negative films, color reversal films, color positivefilms, color photographic paper, color reversal photographic paper,color-sensitive materials for the dye diffusion transfer process or thesilver dye bleach process.

[0467] Of especial interest is a color photographic recording materialcomprising, on a base, at least one blue-sensitive silver halideemulsion layer containing at least one yellow dye providing compound, atleast one green-sensitive silver halide emulsion layer containing atleast one magenta dye providing compound, at least one red-sensitivesilver halide emulsion layer containing at least one cyan dye providingcompound, and customary (non light sensitive) top layer(s) andinterlayers separating the light-sensitive layers.

[0468] The layers of the color photographic material can be arranged invarious orders as is well known in the art.

[0469] The compounds of the formula V can be contained in any of thelayers of the photographic material, i.e. in any of the light sensitivesilver halide emulsion layers or in a non light sensitive layer. For useas a Dox scavenger, the compound of the formula V is preferablycontained in one or more non light sensitive layers. In this case, thelight sensitive layers may contain a lower concentration of a compoundof the formula I or none.

[0470] The compounds of the formula V are preferably incorporated in aninterlayer, especially a non-photosensitive interlayer, adjacent to thegreen-sensitive layer containing a magenta coupler. Preferred colorphotographic materials within this invention are those wherein themagenta coupler is of the pyrazolo-azole type, e.g. as disclosed in U.S.Pat. No. 5,538,840, column 49, line 51, until column 69, line 27, andpublications cited therein; this section of U.S. Pat. No. 5,538,840 ishereby incorporated by reference.

[0471] Also preferred is a color photographic material, wherein thesilver halide emulsion contains at least 95 mol-% AgCl.

[0472] In general, the compounds of the formula V are contained in thephotographic material in an amount from 10 to 1000 mg/m², especiallyfrom 30 to 500 mg/m².

[0473] The compounds of formula V can be milled with polymers (e.g. PVS,polyester, polyvinyl alcohol etc.) and placed in a layer thus preventingtheir migration to adjacent layers. Also, compounds of formula Vcontaining a suitable functional group (e.g. ester, hydroxy) can bereacted with a polymer, e.g. a polyvinyl alcohol or polyester, in orderto attach them chemically. This form will reduce their migratingtendency.

[0474] Typical bases for the photographic material include polymericfilms and paper (including polymer-coated paper). Details regardingsupports and other layers of color photographic recording materials canbe found in Research Disclosure, Item 36544, September 1994.

[0475] Essential constituents of the photographic emulsion layers arebinders, silver halide particles and color couplers. Details regardingthe constituents of the light sensitive layers and other (non lightsensitive) layers such as top layers and interlayers separating thesilver halide emulsion layers can be found in Research Disclosure, Item38957, September 1996.

[0476] The invention therefore also pertains to a color photographicmaterial comprising a compound of the formula V, and to the use of acompound of the formula V as an additive in a color photographicmaterial.

[0477] The invention also partains to a process for preventing migrationof the oxidized developer in a color photographic material from onecolor sensitive layer to another by incorporating a compound of theformula V into said material.

[0478] The compounds of the formula V of the present invention are ofspecial advantage when incorporated into photographic materialscontaining magenta couplers of the pyrazolotriazole class.

[0479] Examples for especially suitable yellow, magenta and cyancouplers to be used in combination with compounds of the presentinvention are as given in U.S. Pat. No. 5,538,840, column 33, line 3,until column 73, line 34, and publications cited therein. These passagesare hereby incorporated by reference.

[0480] The compounds of the formula V which can be used in the contextof this invention can be incorporated into the color photographicrecording material, on their own or together with the color coupler andwith or without further additives, by pre-dissolving them inhigh-boiling organic solvents. Preference is given to the use ofsolvents which boil at higher than 160° C. Typical examples of thesesolvents are the esters of phthalic acid, phosphoric acid, citric acid,benzoic acid or of fatty acids, and also alkylamides and phenols.

[0481] Further details on the structure of the color photographicmaterial of the invention, and the components or further additives whichcan be employed in the novel material, can be found, inter alia, in U.S.Pat. No. 5,538,840, column 27, line 25, to column 33, line 2; andfurther in U.S. Pat. No. 5,538,840 from column 74, line 18, to column106, line 16; and in U.S. Pat. No. 5,780,625, column 12, line 6, untilcolumn 57, line 6, and the publications cited in these 2 references;these passages of U.S. Pat. No. 5,538,840 and U.S. Pat. No. 5,780,625are hereby incorporated by reference. Other useful information, howcompounds of the formula I can be used in photographic material, can betaken from EP-A-0 871 066, page 10, line 10, until page 11, line 32,especially the references cited therein.

[0482] The photographic layers in the material of this invention mayalso include UV absorbers, which screen out the UV light and thereforeprotect the dyes, the couplers or other components againstphotodegradation. Hydroquinone compounds according to this invention maybe contained in those layers where UV absorbers are present.

[0483] UV absorbers preferably to be used in the novel material orwithin the process of present invention include benzotriazoles,2-hydroxybenzophenones, oxanilides, cyanoacrylates, salicylic esters,acrylonitrile derivatives, thiazolines and 2-hydroxyphenyltriazines.

[0484] GB-A-2,319,523 describes from page 49, line 21, until page 73,line 2, further details of the color photographic material, especiallycouplers (page 52, line 1, until page 56, line 22), UV absorbers (page56, line 25, until page 68, line 1) and dark stabilizers (page 68, line2, until page 73, line 2). Preferred UV absorbers of the2-hydroxyphenyltriazine class are also described in detail, for example,in U.S. Pat. No. 5,668,200, column 1, line 30, until column 7, line 55,and as specific examples from column 26, line 31, until column 32, lastline, and, together with some advantageous UV absorbers of thebenzotriazole class, in U.S. Pat. No. 5,300,414, column 2 to column 10,line 54. These sections of U.S. Pat. No. 5,668,200 and U.S. Pat. No.5,300,414 are hereby incorporated by reference.

[0485] The compounds of formula V may be used in combination with anyknown Dox scavengers such as hydrazines, hydrazides, hydroquinones ofe.g. formula HQ-1 or HQ-2; 6-hydroxy-chromanes of e.g. formula A-3, orhydroxylamines of e.g. formula A-4

[0486] As silver halide emulsions it is possible to use customary silverchloride, silver bromide or silver iodide emulsions or mixtures thereof,such as silver chlorobromide and silver chloroiodide emulsions, in whichthe silver halides may have all known crystal forms. The use of silverchloride emulsions is accorded particular importance in the material ofthis novel process. The preparation of such emulsions and theirsensitization are described in Research Disclosure, Item 307105,November 1989.

[0487] The compounds of the formula V may preferably also be used asstabilizers for ethylenically unsaturated resins against prematurepolymerization or crosslinking of the resins during transport orstorage.

[0488] Preferred ethylenically unsaturated resins are for example liquidor resin-like monomers, oligomers, co-oligomers, polymers of co-polymersor mixtures thereof, which possess at least one ethylenicallyunsaturated bond and which are photo-polymerisable or curable with UVlight.

[0489] The following Examples illustrate the invention further. Parts orpercentages relate to weight.

EXAMPLE 1

[0490] Process for the preparation of5,7-di-tert-butyl-3-phenyl-3H-benzofuran-2-one (compound (101), Table1).

[0491] a) Preparation of 2-amino-3-phenyl-5,7-di-tert-butyl-benzofurane(compound (301), Table 3).

[0492] A solution of 0.98 g (20,0 mmol) of sodium cyanide in 2.0 ml ofwater is added to a solution of 3.39 g (10,0 mmol) of2,4-di-tert-butyl-6-(dimethylaminophenyl-methyl)-phenol [compound (201),Table 2, prepared according to Example 2a in WO-A-99/67232] in 10 ml ofsulfolane. The reaction mixture is then maintained at 120° C. for onehour. After cooling to room temperature, the reaction mixture is pouredinto 80 ml tert-butyl-methylether and washed three times with water. Theorganic phases are combined, dried over sodium sulfate and concentratedusing a vacuum rotary evaporator. The residue yields 3.20 g (99%) of2-amino-3-phenyl-5,7-di-tert-butyl-benzofurane (compound (301), Table3), m.p. 174-178° C.

[0493] Compounds (304) to (323) [Table 3] are obtained in analogy toExample 1a using compounds (204) to (223) [Table 2] instead of compound(201).

[0494] b) Preparation of 5,7-di-tert-butyl-3-phenyl-3H-benzofuran-2-one(compound (101), Table 1).

[0495] 4.8 ml (9.58 mmol) of 2N HCl is added at room temperature to asolution of 3.08 g (9.58 mmol) of2-amino-3-phenyl-5,7-di-tert-butyl-benzofurane [compound (301), Table 3,prepared according to Example 1a] in 10 ml iso-propanol and stirred atroom temperature for 90 minutes. The precipitate is filtered and washedwith isopropanol. Crystallization of the residue from isopropanol yields2.62 g (85%) of 5,7-di-tert-butyl-3-phenyl-3H-benzofuran-2-one (compound(101), Table 1), m.p. 116-119° C.

[0496] Compounds (104) to (123) [Table 1] are obtained in analogy toExample 1b using compounds (304) to (323) [Table 3] instead of compound(301).

EXAMPLE 2

[0497] Process for the preparation of5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzo-furan-2-one (compound(102), Table 1).

[0498] a) Preparation of2-amino-5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-benzofurane (compound(302), Table 3).

[0499] A solution of 0.25 g (5,00 mmol) of sodium cyanide in 0.5 ml ofwater is added to a solution of 0.37 g (1,00 mmol) of2,4-di-tert-butyl-6-[dimethylamino-(3,4-dimethylphenyl-methyl)-phenol[compound (202), Table 2, prepared according to Example 1a inWO-A-99/67232] in 5 ml of sulfolane. The reaction mixture is thenmaintained at 120° C. for one hour. After cooling to room temperature,the reaction mixture is diluted with diethyl ether and washed threetimes with water. The organic phases are combined, dried over sodiumsulfate and concentrated using a vacuum rotary evaporator.Crystallisation of the residue from hexane yields 0.28 g (86%) of2-amino-5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-benzofurane (compound(302), Table 3), m.p. 128-130° C.

[0500] b) Preparation of5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one (compound(102), Table 1).

[0501] 0.35 ml (0.70 mmol) of 2N HCl is added at room temperature to asolution of 0.22 g (0.63 mmol) of2-amino-5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-benzofurane [compound(302), Table 3, prepared according to Example 2a] in 5 ml methanol andstirred at room temperature for 2 hours. The reaction mixture is dilutedwith water and extracted three times with ethyl acetate. The organicphases are combined, dried over sodium sulfate and concentrated using avacuum rotary evaporator. Crystallisation of the residue from ethanolyields 200 mg (96%) of5,7-di-tert-butyl-3-(3,4-dimethylphenyl-3H-benzofuran-2-one (compound(102), Table 1), m.p. 130-132° C.

EXAMPLE 3

[0502] Process for the preparation of5,7-di-tert-butyl-3-(3,4-dimethoxyphenyl)-3H-benzofuran-2-one (compound(103), Table 1).

[0503] a) Preparation of2-amino-5,7-di-tert-butyl-3-(3,4-dimethoxyphenyl)-benzofurane (compound(303), Table 3).

[0504] A solution of 0.33 g (6,80 mmol) of sodium cyanide in 0.5 ml ofwater is added to a solution of 0.50 g (1,36 mmol) of2,4-di-tert-butyl-6-[dimethylamino-(3,4-dimethoxyphenyl-methyl)-phenol[compound (203), Table 2, prepared in analogy to Example 1a inWO-A-99/67232] in 5 ml of sulfolane. The reaction mixutre is thenmaintained at 105° C. for one hour. After cooling to room temperature,the reaction mixture is diluted with ethyl acetate and washed threetimes with water. The organic phases are combined, dried over sodiumsulfate and concentrated using a vacuum rotary evaporator.Crystallisation of the residue from hexane yields 0.47 g (95%) of2-amino-5,7-di-tert-butyl-3-(3,4-dimethoxyphenyl)-benzofurane (compound(303), Table 3), m.p. 172-174° C.

[0505] b) Preparation of5,7-di-tert-butyl-3-(3,4-dimethoxyphenyl)-3H-benzofuran-2-one (compound(103), Table 1).

[0506] 0.20 ml (0.40 mmol) of 2N HCl is added at room temperature to asolution of 50 mg (0.13 mmol) of2-amino-5,7-di-tert-butyl-3-(3,4-dimethoxyphenyl)-benzofurane [compound(303), Table 3, prepared according to Example 3a] in 2 ml methanol andstirred at room temperature for one hour. The reaction mixture isdiluted with water and extracted three times with ethyl acetate. Theorganic phases are combined, dried over sodium sulfate and concentratedusing a vacuum rotary evaporator. The residue yields 41 mg (82%) of5,7-di-tert-butyl-3-(3,4-dimethoxyphenyl-3H-benzofuran-2-one (compound(103), Table 1), viscous oil. TABLE 1 No. Compound 101

102

103

104

105

106

107

108

109

110

111

112

113

114

115

116

117

118

119

120

121

122

123

[0507] TABLE 2 No. Compound 201

202

203

204

205

206

207

208

209

210

211

212

213

214

215

216

217

218

219

220

221

222

223

[0508] TABLE 3 No. Compound m.p. (° C.) 301

176-178 302

128-130 303

172-174 304

resin 305

resin 306

128-130 307

 99-100 308

109-111 309

132-134 310

123-125 311

172-173 312

resin 313

101-103 314

127-132 315

156-158 316

resin 317

140-141 318

168-171 319

121-123 320

124-125 321

322

323

EXAMPLE 4

[0509] Stabilization of multiple-extruded polypropylene.

[0510] 1.3 kg of polypropylene powder (Profax 6501), which has beenprestabilized with 0.025% of Irganox®1076 (n-octadecyl3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate) (melt index 3.2 g/10min, measured at 230° C./2.16 kg) are blended with 0.05% of Irganox®1010(pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), 0.05% ofcalcium stearate, 0.03% of DHT 4A® (Kyowa Chemical Industry Co., Ltd.,[Mg_(4.5)Al₂(OH)₁₃CO₃·3.5 H₂O]) and 0.05% of compound of Table 3. Thisblend is then extruded in an extruder having a cylinder diameter of 20mm and a length of 400 mm at 100 rpm, the 3 heating zones being adjustedto the following temperatures: 260, 270, 280° C. The extrudate is cooledby drawing it through a water bath and is then granulated. Thisgranulate is repeatedly extruded. After 3 extrusions, the melt index ismeasured (at 230° C./2.16 kg). A substantial increase in the melt indexdenotes pronounced chain degradation, i.e. poor stabilization. Theresults are summarized in Table 4. TABLE 4 Compound of Melt index after3 Table 1 extrusions — 17.8 301 4.9 302 4.9 311 4.9 313 4.9 319 4.9

EXAMPLE 5

[0511] Stabilization of polyethylene during processing.

[0512] 100 parts of polyethylene powder (Lupolen® 5260 Z) are blendedwith 0.05 part of Irganox® 1010 (pantaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]) and 0.05 partof a compound of Table 3 and the blend is kneaded in a Brabenderplastograph at 220° C. and 50 rpm. During this time the kneadingresistance is recorded continuously as torque. In the course of thekneading time the polymer begins to crosslink after prolonged constancy,as can be determined by the rapid increase in torque. The time takenuntil a marked increase in torque is shown in Table 5 as a measure ofthe stabilizing action. The longer this time is the better thestabilizing action. TABLE 5 Compound of Time until increase Table 1 intorque (min) — 9.7 301 27.4 302 27.4 307 27.3 310 27.4 320 27.3

EXAMPLE 6

[0513] Stabilization of multiple-extruded polypropylene at hightemperature.

[0514] 1.5 kg of polypropylene powder (Profax 6501), which has beenprestabilized with 0.008% of Irganox®1076 (n-octadecyl3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate) (melt index 3.2 g/10min, measured at 230° C./2.16 kg) are blended with 0.05% of lrganox®1010(pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), 0.10% ofcalcium stearate and 0.015 to 0.100% of stabilizer or stabilizer mixtureaccording to Table 6. This blend is then extruded in an extruder havinga cylinder diameter of 20 mm and a length of 400 mm at 100 rpm, the 3heating zones being adjusted to the following temperatures: 280, 320,340° C. The extrudate is cooled by drawing it through a water bath andis then granulated. This granulate is repeatedly extruder. After 5extrusions, the melt index is measured (at 230° C./2.16 kg). Asubstantial increase in the melt index denotes pronounced chaindegradation, i.e. poor stabilization. The results are summarized inTable 6. TABLE 6 Melt index after 5 Concentration in extrusionsStabilizers % (by weight) 280° C. 320° C. 340° C. Irgafos ® 168^(a))0.100 9.8 44.0 80.4 Sandostab ® P-EPQ^(b)) 0.050 6.4 24.1 61.9 Compound(301) 0.015 8.1 19.8 22.7 Irgafos ® 168^(a)) 0.045 7.3 23.1 26.1Compound (301) 0.005 Sandostab ® P-EPQ^(b)) 0.045 5.7 16.0 24.9 Compound(301) 0.005

[0515] For footnotes a) and b) see the end of Table 21.

EXAMPLE 7

[0516] Preparation of polyether/polyurethane soft foams as well as thestabilization thereof.

[0517] Exactly 470 mg (0.3%, based on the polyol) of a stabilizermixture of this invention is dissolved in 157 g of an antioxidant-freepolyether/polyol, Lupranol®2045 (trifunctional poly-ether/polyol havingprimary hydroxyl groups; hydroxyl number 35 mg KOH/g, water content lessthan 0.1%, acid number less than 0.1 mg KOH/g). 10.24 g of a solutionconsisting of 1.74 g Tecostab® (polysilicone supplied by Goldschmidt,Germany], 0.48 g diazabicyclooctane (amine catalyst) and 0.8 g of waterare added and the reaction mixture is stirred vigorously for 60 secondsat 100 rpm. 3.2 g of a solution of 0.32 g of tin octoate (catalyst) in2.9 g of the above polyol is added and the reaction mixture is againstirred vigorously for 60 seconds at 100 rpm. With vigorous stirring, 98g of an isocyanate (Lupranat®80, supplied by BASF; toluylene-2,4- andtoluylene-2,6-diisocyanate mixture) are then added immediately and after6 seconds the mixture is poured into a lined mould and the exothermictemperature is measured during foaming to a foam block. The foam blocksare cooled for 24 hours in a climatic chamber at 5° C. and stored. 2 cmslices are sawed from the center of the blocks and round (cylindrical)test samples are cut therefrom using a boring tool. The samples are agedin a test tube in the presence of air at room temperature and 200° C.for 30 minutes in a preheated alu-block thermostat (dynamic heat test).The yellowing of these test samples is determined as Yellowness Index(YI) according to ASTM D-1925-77. Low YI values denote littlediscoloration, high YI values severe discoloration of the samples. Theresults are summarized in Tables 7 and 8. TABLE 7 Concentration ofstabili- YI YI Example zers in % (by weight) room temp. 200° C. 7a^(i))— 1.0 72.0 7b^(k)) 0.15% Compound (301) 0.5 3.0 0.15% Irganox ®5057^(c)) 7c^(k)) 0.15% Compound (302) 0.5 3.0 0.15% Irganox ® 5057^(c))7d^(k)) 0.15% Compound (318) 0.5 3.0 0.15% Irganox ® 5057^(c))

[0518] TABLE 8 Concentration of stabili- YI YI Example zers in % (byweight) room temp. 200° C. 7e^(i)) — 0.6 70.0 7f^(k)) 0.10% Compound(301) 0.3 2.7 0.10% Irganox ® 5057^(c)) 0.10% Irganox ® 1135^(d))7g^(k)) 0.10% Compound (302) 0.3 2.7 0.10% Irganox ® 5057^(c)) 0.10%Irganox ® 1135^(d)) 7h^(k)) 0.10% Compound (318) 0.3 2.7 0.10% Irganox ®5057^(c)) 0.10% Irganox ® 1135^(d))

[0519] For footnotes c), d), i) and k) see the end of Table 21.

EXAMPLE 8

[0520] Stabilizing polypropylene fibers processed at 300° C.

[0521] 2.0 kg of polypropylene powder (B 10 FB® from Polychim S.A.,France), which has a melt index of 12.0 g/dmin measured in accordancewith DIN 53735 at 230° C. under 2.16 kg, is homogenized with 0.05% ofcalcium stearate and with the stabilizers indicated in Tables 9 and 10for 2 minutes in a high-speed mixer. This mixture is extruded at 60revolutions per minute in an extruder having a barrel diameter of 20 mmand a length of 400 mm, the three heating zones being set at thefollowing temperatures: 200, 220 and 220° C. The extrudate is passedthrough a water bath for cooling and then granulated. These granules areprocessed to give a multifilament fiber. This is done using asingle-screw extruder with a melt pump and a 37-hole spinning head. Themaximum processing temperature is 300° C.

[0522] A portion of the unstretched fiber thus obtained is pressed for 6minutes at 230° C. to form a sheet with a thickness of 2 mm. The meltindex (MFI, melt flow index) of this sheet is measured in accordancewith DIN 53735 at 230° C. and 2.16 kg. A large increase in the meltindex denotes severe chain degradation and thus poor stabilization. Theresults are compiled in Table 9.

[0523] Another portion of the unstretched fiber thus obtained is treatedwith a lubricant (Limanol®P 25, Schill und Seilacher, Böblingen,Germany) and subjected to preliminary drawing. This preliminary drawingleads to a fiber strand having a linear density of 416 g/90 m. Thismeans that a fiber strand 90 m in length has a weight of 416 g. In afurther operation, this fiber strand is again drawn at 120° C. by afactor of 3.2 using a drawing apparatus. This leads to a fiber strandhaving a linear density of 130 g/90 m.

[0524] A portion of this fiber strand is used to produce a knitted tube.The yellowness index ( YI₁) of this knitted tube is determined inaccordance with ASTM D 1925-77. Low YI₁ values denote littlediscoloration, high YI₁ values severe discoloration of the samples. Theresults are compiled in Table 9. This knitted tube is exposed in thepresence of from 4 to 6 ppm nitrogen dioxide (NO₂) at 40° C. and 87%relative atmospheric humidity for 48 hours in accordance with AATCC 164.The yellowness index (YI₂) of this exposed knitted tube is determined inaccordance with ASTM D 1925-77. Low YI₂ values denote littlediscoloration, high YI₂ values severe discoloration of the samples. Theresults are compiled in Table 9.

[0525] Another portion of the fiber strand is used to carry out an ovenageing test at 100° C. In this test, a measurement is made, in days, ofthe time taken for the fiber strand to tear under the test conditions.The longer the period before tearing of the fiber strand, the better thestabilization. The results are compiled in Table 10.

[0526] Another portion of the unstretched fiber is pressed for 6 minutesat 230° C. to form a thin film with a thickness of 0.10 mm. This film issubjected to a Xenon test in accordance with DIN 53387. In this test,the film is exposed in a Xenon 1200 weathering apparatus until acarbonyl index of 0.25 is observed in the wavelength range from 1760 to1680 cm⁻¹. The larger the number, the better the stabilization. Theresults are compiled in Table 10. TABLE 9 YI₁ YI₂ MFI after after afterspin- NO₂ expo- spin- Example Stabilizers ning sure ning 8a^(i)) — 0.31.4 109.0 8b^(k)) 0.100% Compound (301) 1.5 5.4 34.5 0.050% Tinuvin ®622^(e)) 8c^(k)) 0.100% Compound (301) 1.6 4.7 33.0 0.050% Chimassorb ®944^(f)) 8d^(k)) 0.100% Compound (301) 0.8 4.7 31.9 0.050% Chimassorb ®119^(g)) 8e^(k)) 0.075% Compound (301) 0.8 4.7 32.0 0.050% Tinuvin ®622^(e)) 0.075% Irgafos ® 168^(a)) 8f^(k)) 0.075% Compound (301) 1.5 4.832.9 0.050% Chimassorb ® 944^(f)) 0.075% Irgafos ® 168^(a)) 8g^(k))0.075% Compound (301) 1.5 4.7 31.9 0.050% Chimassorb ® 944^(f)) 0.075%Irgafos ® 38^(h)) 8h^(k)) 0.075% Compound (301) 1.5 4.7 32.6 0.050%Chimassorb ® 119^(g)) 0.075% Irgafos ® 168^(a))

[0527] For footnotes a), e), f), g), h), i) and k) see the end of Table21. TABLE 10 Oven ageing Xenon test Example Stabilizers (days) (hours)8a^(i)) —  1  200 8c^(k)) 0.100% Compound (306) 39 1350 0.050%Chimassorb ® 944^(f)) 8d^(k)) 0.100% Compound (306) 39 1540 0.050%Chimassorb ® 119^(g)) 8f^(k)) 0.075% Compound (306) 39 1340 0.050%Chimassorb ® 944^(f)) 0.075% Irgafos ® 168^(a)) 8g^(k)) 0.075% Compound(306) 39 1360 0.050% Chimassorb ® 944^(f)) 0.075% Irgafos ® 38^(h))8h^(k)) 0.075% Compound (306) 39 1500 0.050% Chimassorb ® 119^(g))0.075% Irgafos ® 168^(a))

[0528] For footnotes a), f), g), h), i) and k) see the end of Table 21.

EXAMPLE 9

[0529] Preparation of polyolefin hollow articles by the rotomoldingprocess.

[0530] 100 Parts of low density polyethylene, copolymerized with hexene(PE-LLD), type Quantum® Petrothene® GA-635-661, having a melt flow indexof 6.5 g/10 min and a density of 0.935 g/cm³, are mixed with 0.170 partof Chimassorb® 944 [formula see footnote (b) after Table 21], 0.050 partof zinc stearate and the stabilizers cited in Tables 11 and 12 at 232°C. in a Superior/MPM Extruder, fitted with a 24:1 Maddock type UD screw,at 100 revolutions per minute. The polymer is then ground. The particlesize of the polymer is from 150 to 500 μm. Owing to the larger surfaceof the particles obtained by grinding, the heat can be absorbed faster,which goes hand in hand with a lower energy consumption.

[0531] The actual rotomolding process or rotational molding process,which permits the production of fairly large three-dimensional solids,is carried out in a Clamshell type rotomolder FSP M20. In this machine,an aluminium mold, which is mounted on an arm and into which the plasticsample is filled, is heated with a gas burner with circulation of thehot air over 5 minutes to 316° C., or over 6 minutes to 329° C., and isthen kept at this temperature for a specific time (see Tables 11 and12). Subsequently, the oven is opened and the mold is cooled first for 7minutes with circulating air, then for 7 minutes by spraying with waterand finally for another 2 minutes with circulating air. During theentire heating and cooling process, the mold, which is mounted on twoaxes at right angles to each other, is rotated, the speed of the mainaxis being kept at 6 revolutions per minute and the rotational ratiobeing 4.5:1. After cooling, the lid of the mold is opened and theresultant hollow article is taken out. The yellowness index (YI) of theexterior of the molded articles is determined according to ASTM D1925-70. Low YI values denote little discoloration, high YI valuesstrong discoloration of the samples. The less discoloration, the moreeffective the stabilizer. The results are summarized in Tables 11 and12. TABLE 11 Rotomolding at 316° C. Yellowness Index after ExampleStabilizer 8 minutes 10 minutes 9a^(i)) 0.05% Irganox ® 1010^(l)) 6.317.8 0.10% Irgafos ® 168^(a)) 9b^(k)) 0.02% compound (301) 4.3 5.3 0.08%Irgafos ® 168^(a))

[0532] TABLE 12 Rotomolding at 329° C. Yellowness Index after ExampleStabilizer 6 minutes 8 minutes 9c^(i)) 0.05% Irganox ® 1010^(l)) 4.116.7 0.10% Irgafos ® 168^(a)) 9d^(k)) 0.02% compound (301) 4.1 5.8 0.08%Irgafos ® 168^(a))

[0533] For footnotes a), i), k) and l) see the end of Table 21.

EXAMPLE 10

[0534] Stabilisation of polyethylene which is in permanent contact withwater.

[0535] 0.10% by weight of calcium stearate and a stabilizer mixturecomprising 0.10% by weight of Irganox®1010 (pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), 0.05% byweight of lrgafos®68 (tris(2,4-di-tert-butylphenyl)phosphite) and 0.05%by weight of compound (302) (Table 3) is added dry to a polyethylenepolymer (Hostalene® CRP 100; PE-HD) taken direct from a reactor and areincorporated therein in a Pappenmaier mixer (type 20) within 2 minutes.

[0536] In an extruder, of Schwabenthan, the stabilized polyethylene ishomogenised and processed to granulate. For the extraction tests inwater, 200 mm by 150 mm by 2 mm test plates are pressed from thegranulate of the individual formulations using a table press. To easethe demoulding of the test plates, the pressing process is carried outbetween two aluminium foils.

[0537] The stabilizer extraction tests are carried out with deionisedwater. Preliminary heating of the extraction vessels is carried out in acirculating air oven, of Heraeus (Hanau, Germany), at a maximumtemperature deviation of 1.5° C. Glass vessels are used for extractiontests below the boiling point of water, such as at 80° C. Owing to therisk of oversaturating the water with stabilizers, the amount of liquidused for the tests is fixed at c. 400 ml per c. 70 g of polymer and thewater is replaced with fresh water at regular intervals, i.e. whenever asample is taken.

[0538] The test plates are subjected to the above test conditions for 50days at 80° C. Upon termination of the extraction test, the residualstabilizer content and the oxidation induction time of the test platesare determined.

[0539] The residual content of sterically hindered phenol, Irganox®1010,is determined using an internal standard in an HPLC appliance of theSpectra Physics SP 8800 type, equipped with autosampler and UV/VISdetector of the Spectra 200 type. The chromatography is carried out atroom temperature using a Hyperchrome 125×4.6 mm type column which isfilled with Nucleosil C 185 μm. The injection volume is 14 μl at a flowrate of 1.5 ml/minute. UV detection takes place at 270 nm.

[0540] The oxidation induction time which is determined using a“DuPont-instrument 910 Differential Scanning Calorimeter”, of TAInstruments (Alzenau, Germany), and taking a 5 to 10 mg amount ofsample, describes the time in minutes at constant thermal stress (190°C./O₂) up to the start of the complete degradation of the polyethylenesample. The longer the oxidation induction time, the better stabilizedthe polyethylene and the more stable is the polyethylene againstextracting water with which it is in permanent contact. The results showthat the stability of polyolefins which are in permanent contact withextracting media is improved if they contain the compound (302)according to the instant invention as stabilizer.

EXAMPLE 11

[0541] Measuring the discoloration of powder coatings based on acarboxy-functional polyester and cured in electric and gas ovens.

[0542] To prepare the powder coating composition based on acarboxy-functional polyester, components 1 to 6 (formulation withoutadditives) or components 1 to 7 (formulation containing the stabilizers)are employed in the sequence indicated (cf. Table 13). TABLE 13 Examples(amount in grams) Components 1a 1b to 1i 1. Crylcoat ® 360^(a)) 591 5912. Araldit ® GT 7004^(b)) 394 394 3. Octadecyltrimethylammoniumbromide^(c)) 3.6 3.6 4. Resiflow ® PV 88^(d)) 12 12 5. Benzoin^(e)) 3 36. Titanium dioxide type R-KB-5^(f)) 500 500 7. Stabilizers (see Tables14 and 15) — 6 Total: 1503.6 1509.6

[0543] The components weighed out in this way are mixed using aplanetary stirrer. The mixture is then extruded on a prism extruder at300 revolutions/minute and at 100° C. and is rolled out. The powdercoating composition is coarsely comminuted using a bench cutter and isground in a Retsch ZM-1 ultracentrifugal mill with a 0.75 mmannular-perforation screen at 15,000 revolutions/minute. Finally, thepowder is passed through a 30 μm screen on a centrifugal screeningmachine.

[0544] The finished powder coating composition is sprayedelectrostatically to a coat thickness of 70 μm onto aluminium panelsusing an ESB-Wagner corona cup gun at 60 kV. Some of the coated panelsare cured at 180° C. for 90 minutes in an electric oven. The remainingcoated panels are cured at 180° C. for 45 minutes in a gas oven with anNO₂ content of 20 ppm. The yellowness index (YI) of the samples isdetermined in accordance with ASTM D 1925-70. Low YI values denotelittle discoloration, high YI values denote severe discoloration of thesamples. The less the discoloration, the more effective the stabilizer.The results are summarized in Tables 14 and 15. TABLE 14 Curing for 90minutes in an electric oven at 180° C. Ex- am- Stabilizers Yellownessindex after 90 minutes ple (% rel. to components 1 to 5) (ASTM D1925-70) 11a^(i))    — 3.1 11b^(k)) 0.60% Compound (301) 2.8 11c^(k))0.50% Irgafos ® 168^(a)) 2.8 0.10% Compound (301) 11d^(k)) 0.15%Irgafos ® 168^(a)) 2.8 0.15% HALS mixture^(m)) 0.30% Compound (301)11e^(k)) 0.15% lrgafos ® 168^(a)) 2.8 0.15% Irganox ® 1010^(l)) 0.30%Compound (301)

[0545] TABLE 15 Curing for 45 minutes in a gas oven at 180° C. Ex- am-Stabilizers Yellowness index after 90 minutes ple (% rel. to components1 to 5) (ASTM D 1925-70) 11f^(i))    — 4.2 11g^(k)) 0.60% Compound (301)3.5 11h^(k)) 0.50% Irgafos ® 168^(a)) 3.5 0.10% Compound (301) 11i^(k))0.15% Irgafos ® 168^(a)) 3.4 0.15% HALS mixture^(m)) 0.30% Compound(301)

[0546] For footnotes a), m), k) and l) see the end of Table 21.

EXAMPLE 12

[0547] Stabilizing polypropylene in the case of multiple extrusion andat especially high temperatures.

[0548] 1.5 kg of polypropylene powder (Profax®6501), which has beeninitially stabilized with 0.008% of Irganox®1076 (n-octadecyl3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate) (with a melt index of3.2 measured at 230° C. and under 2.16 kg), are mixed with 0.10% ofcalcium stearate and 0.015 to 0.20% of the stabilizers listed in Table16. This mixture is extruded in an extruder having a barrel diameter of20 mm and a length of 400 mm at 100 revolutions per minute, the maximumextruder temperature being set at 280, 300, 320 and 340° C. For cooling,the extrudate is drawn through a water bath and then granulated. Thesegranules are extruded repeatedly. After 5 extrusions, the melt index ismeasured (at 230° C. under 2.16 kg). A large increase in the melt indexdenotes severe chain breakdown and hence poor stabilization. The resultsare summarized in Table 16. TABLE 16 Amount Melt index ExampleStabilizers (% by wt.) after 5 extrusions 12a^(i)) Irgafos ® 168^(a))0.10 18.4  Irganox ® 1010^(l)) 0.10 Chimassorb ® 944^(f)) 0.20 12b^(k))Compound (302)  0.015 8.9 Irgafos ® 168^(a)) 0.10 Irganox ® 1010^(l))0.05 Chimassorb ® 944^(f)) 0.10 12c^(k)) Compound (302)  0.015 8.7Irgafos ® 168^(a)) 0.10 Irganox ® 1010^(l)) 0.05 Chimassorb ® 119^(g))0.10

[0549] For footnotes a), f), g), i), k) and l) see the end of Table 21.

EXAMPLE 13

[0550] Stabilization of polycarbonate.

[0551] 1.0 kg of a polycarbonate powder which has been dried for 8 hoursat 120° C. in a vacuum drying oven (Lexan®115, of General Electric) and0.1 to 0.6 g (0.01 to 0.06%) of the stabilizers listed in Table 17 aremixed for 2 minutes in a Henschel mixer. This mixture is then extrudedin a Schwabenthan extruder at a maximum of 280° C. The polymer string isthen granulated. Using an injection moulding machine, plates having alayer thickness of 2 mm are then moulded from the granulate so obtainedat a maximum of 300° C. These plates are then aged in a circulating airoven at 135° C. for 2000 hours. The yellowness index (YI) of theseplates is then determined according to ASTM D 1925-70 and thetransmission is determined in percent at 450 nm. Low YI values denotelittle discoloration, high YI values high discoloration of the patterns.The less discoloration, the more effective the stabilizer. The higherthe transmission values, the more effective the stabilizer. The resultsare compiled in Tables 17 and 18. TABLE 17 Yellowness Ex- indexYellowness index am- prior to after 2000 hours at ple Stabilizersoven-ageing 135° C. 13a^(i))    — 4.1 25.5 13b^(i)) 0.05% Irgafos ®168^(a)) 3.5 23.9 13c^(k)) 0.01% Compound (301) 3.5 16.6 13d^(k)) 0.01%Compound (314) 3.5 15.5 13e^(k)) 0.05% Irgafos ® 168^(a)) 3.4 15.3 0.01%compound (301) 13f^(k)) 0.05% Irgafos ® 168^(a)) 3.4 15.0 0.01% compound(314)

[0552] TABLE 18 Yellowness Ex- index Yellowness index am- prior to after2000 hours at ple Stabilizers oven-aging 135° C. 13a^(i))    — 84.8 76.213b^(i)) 0.05% Irgafos ® 168^(a)) 84.8 77.9 13c^(k)) 0.01% Compound(301) 85.9 81.2 13d^(k)) 0.01% Compound (314) 85.9 81.5 13e^(k)) 0.05%Irgafos ® 168^(a)) 85.9 81.4 0.01% Compound (301) 13f^(k)) 0.05%Irgafos ® 168^(a)) 86.0 81.4 0.01% compound (314)

[0553] For footnotes a), i) and k) see the end of Table 21.

EXAMPLE 14

[0554] Stabilization of polycarbonate.

[0555] 1.0 kg of a polycarbonate powder which has been dried for 8 hoursat 120° C. in a vacuum drying oven (Lexan®145, of General Electric) ischarged with the stabilizers listed in Table 19 and is mixed for 2minutes in a Henschel mixer. This mixture is then extruded in aSchwabenthan extruder at a maximum of 280° C. The polymer string is thengranulated. Using an injection moulding machine, plates having a layerthickness of 2 mm are then moulded from the granulate so obtained at amaximum of 300° C. These plates are then aged in a circulating air ovenat 135° C., the time in hours until the yellowness index (YI) reaches avalue of 20 according to ASTM D 1925-70 being measured. The longer thetime, the more effective the stabilizer. The results are compiled inTable 19. TABLE 19 Time in hours at Example Stabilizers 135° C. to Y1 =20 14a^(i))    — 1570 14b^(i)) 0.05% Irgafos ® 168^(a)) 2010 14c^(k))0.006% Compound (308) 2350 0.022% Irgafos ® 168^(a)) 0.012% Irganox ®1076^(n)) 14d^(k)) 0.009% Compound (308) 2355 0.034% Irgafos ® 168^(a))0.017% Irganox ® 1076^(n))

[0556] For footnotes a), i), k) and n) see the end of Table 21.

EXAMPLE 15

[0557] Stabilization of polyesters.

[0558] 2.5 kg of a polyester which has been dried for 12 hours at 120°C. in a vacuum drying oven (Polyclear® T86, of Hoechst) is charged withthe stabilizers listed in Table 20 and is mixed for 2 hours in aHenschel mixer. This mixture is then extruded in a Schwabenthan extruderat a maximum of 275° C. The polymer string is then granulated. Thegranulate so obtained is dried for another 12 hours in a vacuum dryingoven. In a double determination, 500 mg of the granulate is heated over10 minutes to 290° C. and is stored for 1 hour under pure oxygen in arancimate at 290° C. The resulting gaseous separation products arecontinuously led into an aqueous collecting solution and theconductivity (μS) of this solution is continuously measured. Lowconductivity values signify that few separation products are formed,high conductivity values signify that very many separation products areformed. The lower the conductivity values, the more effective thestabilizer. The results are compiled in Table 20. TABLE 20 ExampleStabilizers Conductivity (μS) 15a^(i)) — 46 15b^(k)) 0.20% Compound(302) 33

[0559] For footnotes i) and k) see the end of Table 21.

EXAMPLE 16

[0560] Stabilization of light-colored SBR-vulcanisate (ozone atmospherefor 48 hours).

[0561] 100 parts by weight of Cariflex®S-1502 (styrene/butadiene rubber,Shell) are processed at 60° C., in a mixing mill, with 30.0 parts byweight of Kronos®CL 220 [titanium dioxide (pigment), Kronos Titan GmbH],30.0 parts by weight of Aktisil®MM [kaolin (filler), Hoffmann Mineral,Neuburg/Donau], 5.0 parts by weight of Naftolen®N 401 [plasticizer,Metaligesellschaft], 10.0 parts by weight of zinc oxide [vulcanizationactivator], 2.0 parts by weight of stearic acid [vulcanizationactivator], 2.0 parts by weight of sulfur [vulcanizing agent], 1.0 partby weight of Vulkacit®MOZ [vulcanisation accelerator, Bayer], 0.25 partby weight of Vulkacit®Thiuram [vulcanization accelerator, Bayer] and 1.0part by weight of the stabilizer to be tested according to Table 24, toform a homogeneous mixture, the vulcanization system (sulfur,Vulkacit®MOZ and Vulkacit®Thiuram) not being added until the end of themixing process. The mixture is vulcanized in electrical vulcanizationpresses at 150° C. until T95 is reached in the rheometer curves to formelastomer plates 2 mm thick, 21 cm long and 8.0 cm wide.

[0562] Some of the elastomer plates so obtained are tested for theaction of ozone according to the ASTM standard D 3395-86 while subjectto dynamic elongation. In this test, the plates are first stored for 30days in a standard atmosphere [23/50 SN-ISO 291]. Test specimensmeasuring 20 cm by 1 cm are then punched out and exposed to an ozoneatmosphere for 48 hours (ozone content: 50 pphm; temperature: 40° C.;humidity: 50 % rel.; elongation: 0 to 25%; elongation rate: 0.5 Hz;number of load cycles: approximately 173 000). The test plates are thenassessed for crack formation according to ASTM D 3395-86. Grade 0denotes no cracks; grade 1 denotes narrow flat cracks; grade 2 denotesmoderately broad, moderately deep cracks, clearly visible; grade 3denotes broad and deep cracks. The lower the grade number, the betterthe stabilization of the elastomer plates. The results are compiled inTable 21.

[0563] The remaining elastomer plates are stored for 3 weeks at roomtemperature in a standard laboratory atmosphere in diffuse daylight. TheΔL-color of those plates is then determined according to DIN 6167, whichcorresponds to a scale of from 0 to 100. No discoloration is indicatedby a value of 100. The results are compiled in Table 21. TABLE 21 Ex-Crack formation ΔL-color am- according to according to ple StabilizerASTM D 3395-86 DIN 6167 16a^(l))    — grade 1-2 94 16b^(l)) 1.0 phr^(u))Vulkanox ® 4010^(t)) grade 0 70 16c^(k)) 1.0 phr^(u)) Compound (301)grade 0-1 94

[0564] a) lrgafose®168 (Ciba Specialty Chemicals Inc.) istris(2,4-di-tert-butylphenyl)phosphite.

[0565] b) Sandostab®P-EPQ (Clariant) istetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene diphosphonite.

[0566] c) Irganox®5057 (Ciba Specialty Chemicals Inc.) is a secondaryamine antioxidant and is a technical mixture, obtained by reaction ofdiphenylamine with diisobutylene, comprising

[0567] a′) 3% of diphenylamine;

[0568] b′) 14% of 4-tert-butyidiphenylamine;

[0569] c′) 30% of compounds of the group

[0570] i) 4-tert-octyidiphenylamine,

[0571] ii) 4,4′-di-tert-butyidiphenylamine,

[0572] iii) 2,4,4′-tris-tert-butyldiphenylamine;

[0573] d′) 29% of the compounds of the group

[0574] i) 4-tert-butyl-4′-tert-octyidiphenylamine,

[0575] ii) o,o′-, m,m′- or p,p′-di-tert-octyldiphenylamine,

[0576] iii) 2,4-di-tert-butyl-4′-tert-octyidiphenylamine;

[0577] e′) 24% of the compounds of the group

[0578] i) 4,4′-di-tert-octyidiphenylamine and

[0579] ii) 2,4-di-tert-octyl-4′-tert-butyldiphenylamine.

[0580] d) Irganox®1135 (Ciba Specialty Chemicals Inc.) is a phenolicantioxidant of the formula A-1.

[0581] e) Tinuvin®622 (Ciba Specialty Chemicals Inc.) is a compound ofthe formula H1 in which the average molecular weight is about 3000.

[0582] f) Chimassorb®944 (Ciba Specialty Chemicals Inc.) denotes linearor cyclic condensation products prepared fromN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylendiamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine and is a compound of theformula H2 in which the average molecular weight is about 2500.

[0583] g) Chimassorb®119 (Ciba Specialty Chemicals Inc.) denotescondensation products prepared from2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane and is a compound of the formulaH3

[0584] in which R′=

[0585] h) Irgafos®38 (Ciba Specialty Chemicals Inc.) is a compound ofthe formula P-1.

[0586] i) Comparison Example.

[0587] k) Example of this invention.

[0588] l) Irganox®1010 (Ciba Specialty Chemicals Inc.) denotes thepentaerythritol ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionicacid.

[0589] m) HALS mixture is a 1:1 mixture of Tinuvin®622 [Ciba SpecialtyChemicals Inc.; see footnote e)] and Chimassorb®119 (Ciba SpecialtyChemicals Inc.; see footnote g)].

[0590] n) Irganox®1076 (Ciba Specialty Chemicals Inc.) denotes acompound of formula A-2.

[0591] t) Vulkanox®4010 (Bayer) denotes 4-isopropylamino-diphenylamineof formula A.

[0592] u) phr denotes “parts per hundred of rubber”.

What is claimed is:
 1. A process for the preparation of compounds offormula I

wherein, when n is 1, R₁ is naphthyl, phenanthryl, anthryl,5,6,7,8-tetrahydro-2-naphthyl, thienyl, benzo[b]thienyl,naphtho[2,3-b]thienyl, thianthrenyl, furyl, benzofuryl, isobenzofuryl,dibenzofuryl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl,pyrazolyl, pyrazinyl, pyridyl, pyrimidinyl, pyridazinyl, indolizinyl,isoindolyl, indolyl, indazolyi, purinyl, quinolizinyl, isoquinolyl,quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl,cinnolinyl, pteridinyl, carbazolyl, β-carbolinyl, phenanthridinyl,acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl,phenothiazinyl, isoxazolyl, furazanyl, biphenyl, terphenyl, fluorenyl orphenoxazinyl, each of which is unsubstituted or substituted by fluorine,hydroxy, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, C₁-C₁₈alkylthio,di-(C₁-C₄alkyl)amino, phenyl, benzyl, benzoyl or by benzoyloxy or R₁ isa radical of formula II or III

when n is 2, R₁ is phenylene or naphthylene each unsubstituted orsubstituted by C₁-C₄alkyl or by fluorine; or is —R₆—X—R₇—, R₂, R₃, R₄and R₅ are each independently of the others hydrogen, fluorine, hydroxy,C₁-C₂₅-alkyl, C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substitutedphenyl, unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl;C₁-C₁₈alkoxy, C₁-C₁₈alkylthio, C₁-C₄alkylamino, di(C₁-C₄alkyl)amino,C₁-C₂₅alkanoyloxy, C₁-C₂₅alkanoylamino; C₃-C₂₅alkanoyloxy interrupted byoxygen, sulfur or by

C₆-C₉cycloalkylcarbonyloxy, benzoyloxy or C₁-C₁₂alkyl-substitutedbenzoyloxy, or furthermore the radicals R₂ and R₃ or the radicals R₃ andR₄ or the radicals R₄ and R₅, together with the carbon atoms to whichthey are bonded, form a benzo ring, R₄ is additionally —(CH₂)_(p)—COR₉or —(CH₂)_(q)OH or, when R₃ and R₅ are hydrogen, R₄ is additionally aradical of formula IV

wherein R₁ is as defined above for the case where n=1, R₆ and R₇ areeach independently of the other phenylene or naphthylene eachunsubstituted or substituted by C₁-C₄alkyl, R₈ is C₁-C₈alkyl, R₉ ishydroxy, $\left\lbrack {{—O}^{-}\frac{1}{r}M^{r +}} \right\rbrack,$

C₁-C₁₈alkoxy or

R₁₀ and R₁₁ are each independently of the other hydrogen, CF₃,C₁-C₁₂alkyl or phenyl, or R₁₀ and R₁₁, together with the carbon atom towhich they are bonded, form a C₅-C₈cycloalkylidene ring unsubstituted orsubstituted by from 1 to 3 C₁-C₄alkyl groups; R₁₂ and R₁₃ are eachindependently of the other hydrogen or C₁-C₁₈alkyl, R₁₄ is hydrogen orC₁-C₁₈alkyl, R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ are each independently of theothers hydrogen, halogen, fluoro-substituted C₁-C₁₂alkyl; —CN,

—SO₂R₄₆, SO₃R₄₆, hydroxy, C₁-C₂₅alkyl; C₂-C₂₅alkyl interrupted byoxygen, sulfur or by

C₁-C₂₅alkoxy; C₂-C₂₅alkoxy interrupted by oxygen, sulfur or by

C₁-C₂₅alkylthio, C₇-C₉phenylalkyl, C₇-C₉phenylalkoxy, unsubstituted orC₁-C₄alkyl-substituted phenyl; unsubstituted or C₁-C₄alkyl-substitutedphenoxy; unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl;unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkoxy;di(C₁-C₄alkyl)amino, C₁-C₂₅alkanoyl; C₃-C₂₅alkanoyl interrupted byoxygen, sulfur or by

C₁-C₂₅alkanoyloxy; C₃-C₂₅alkanoyloxy interrupted by oxygen, sulfur or by

C₁-C₂₅alkanoylamino, C₆-C₉cycloalkylcarbonyl,C₆-C₉cycloalkylcarbonyloxy, benzoyl or C₁-C₁₂alkyl-substituted benzoyl;benzoyloxy or C₁-C₁₂alkyl-substituted benzoyloxy;

R₂₄ is hydrogen, C₁-C₄alkyl, or unsubstituted or C₁-C₄alkyl-substitutedphenyl, R₂₅ and R₂₆ are hydrogen, C₁-C₄alkyl or phenyl, with the provisothat at least one of the radicals R₂₅ and R₂₆ is hydrogen, R₂₇ and R₂₈are each independently of the other hydrogen, C₁-C₄alkyl or phenyl, R₂₉is hydrogen or C₁-C₄alkyl, R₃₀ is hydrogen, unsubstituted orC₁-C₄alkyl-substituted phenyl; C₁-C₂₅alkyl; C₂-C₂₅alkyl interrupted byoxygen, sulfur or by

C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl radical byfrom 1 to 3 C₁-C₄alkyl groups; or C₇-C₂₅phenylalkyl interrupted byoxygen, sulfur or by

and unsubstituted or substituted on the phenyl radical by from 1 to 3C₁-C₄alkyl groups, R₃₁ is hydrogen or C₁-C₄alkyl, R₃₂ is hydrogen,C₁-C₂₅alkanoyl; C₃-C₂₅alkanoyl interrupted by oxygen, sulfur or by

C₂-C₂₅alkanoyl substituted by a di(C₁-C₆alkyl) phosphonate group;C₆-C₉-cycloalkylcarbonyl, thenoyl, furoyl, benzoyl orC₁-C₁₂alkyl-substituted benzoyl;

R₃₃ is hydrogen or C₁-C₈alkyl, R₃₄ is a direct bond, C₁-C₁₈alkylene;C₂-C₁₈alkylene interrupted by oxygen, sulfur or by

C₂-C₂₀alkylidene, C₇-C₂₀phenylalkylidene, C₅-C₈cycloalkylene,C₇-C₈bicycloalkylene, unsubstituted or C₁-C₄alkyl-substituted phenylene,

R₃₅ is hydroxy,$\left\lbrack {{—O}^{-}\frac{1}{r}M^{r +}} \right\rbrack,$

C₁-C₁₈alkoxy or

R₃₆ is oxygen, —NH— or

R₃₇ is C₁-C₁₈alkyl or phenyl, R₄₂ is hydrogen, hydroxy,$\left\lbrack {{—O}^{-}\frac{1}{r}M^{r +}} \right\rbrack,$

C₁-C₂₅alkyl, C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substitutedphenyl; unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl; orC₃-C₂₅alkyl which is interrupted by oxygen, sulfur or

R₄₃ is C₁-C₂₅alkyl, C₇-C₉phenylalkyl, unsubstituted orC₁-C₄alkyl-substituted phenyl; unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; or C₃-C₂₅alkyl which is interrupted by oxygen, sulfuror

R₄₄ and R₄₅ are each independently of one another hydrogen, C₁-C₂₅alkyl,hydroxyl-substituted C₂-C₂₄alkyl; C₃-C₂₅alkyl which is interrupted byoxygen, sulfur or

C₇-C₉-phenylalkyl which is unsubstituted or is substituted on the phenylring by C₁-C₄alkyl; or C₃-C₂₄alkenyl; or R₄₄ and R₄₅, together with thenitrogen atom to which they are attached, form a 5-, 6- or 7-memberedheterocyclic ring which is unsubstituted or is substituted by C₁-C₄alkylor is interrupted by oxygen, sulfur or

R₄₆ is hydrogen or C₁-C₂₅alkyl, M is an r-valent metal cation, X is adirect bond, oxygen, sulfur or —NR₁₄—, n is 1 or 2, p is 0, 1 or2, q is1, 2, 3, 4, 5 or 6, r is 1, 2 or 3, and s is 0, 1 or 2, which processcomprises hydrolyzing a compound of formula V

wherein R₁ and n are as defined above, R₂, R₃, R′₄ and R₅ are eachindependently of the others hydrogen, fluorine, hydroxy, C₁-C₂₅alkyl,C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substituted phenyl,unsubstituted or C₁-C₄alkyl-substituted C₅-C₈-cycloalkyl; C₁-C₁₈alkoxy,Cl-C₁₈alkylthio, C₁-C₄alkylamino, di(C₁-C₄alkyl)amino,C₁-C₂₅alkanoyloxy, C₁-C₂₅alkanoylamino; C₃-C₂₅alkanoyloxy interrupted byoxygen, sulfur or by

C₆-C₉cycloalkylcarbonyloxy, benzoyloxy or C₁-C₁₂alkyl-substitutedbenzoyloxy, or furthermore the radicals R₂ and R₃ or the radicals R₃ andR′₄ or the radicals R′₄ and R₅, together with the carbon atoms to whichthey are bonded, form a benzo ring, R′₄ is additionally —(CH₂)_(p)—COR₉or —(CH₂)_(q)OH or, when R₃ and R₅ are hydrogen, R′₄ is additionally aradical of formula VI

wherein R₁ is as defined above for the case where n=1, in an aqueoussolvent in the presence of an acid.
 2. A process according to claim 1,wherein, when n is 2, R₁ is phenylene or —R₆—X—R₇—, R₆ and R₇ arephenylene, X is oxygen or —NR₁₄—, and R₁₄ is C₁-C₄alkyl.
 3. A processaccording to claim 1, wherein R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ are eachindependently of the others hydrogen, chloro, bromo, fluoro-substitutedC₁-C₁₂alkyl; —CN,

—SOR₄₆, —SO₂R₄₆, SO₃R₄₆, hydroxy, C₁-C₁₈alkyl; C₂-C₁₈alkyl interruptedby oxygen or by sulfur; C₁-C₁₈alkoxy; C₂-C₁₈alkoxy interrupted by oxygenor by sulfur; C₁-C₁₈alkylthio, C₇-C₉phenylalkyl, C₇-C₉phenylalkoxy,unsubstituted or C₁-C₄alkyl substituted phenyl; phenoxy, cyclohexyl,C₅-C₈cycloalkoxy, di(C₁-C₄alkyl)amino, C₁-C₁₂alkanoyl; C₃-C₁₂alkanoylinterrupted by oxygen or by sulfur; C₁-C₁₂alkanoyloxy; C₃-C₁₂alkanoyloxyinterrupted by oxygen or by sulfur; C₁-C₁₂alkanoylamino,cyclohexylcarbonyl, cyclohexylcarbonyloxy, benzoyl orC₁-C₄alkyl-substituted benzoyl; benzoyloxy or C₁-C₄alkyl-substitutedbenzoyloxy;

R₂₄ is hydrogen or C₁-C₄alkyl, R₂₅ and R₂₆ are hydrogen or C₁-C₄alkyl,with the proviso that at least one of the radicals R₂₅ and R₂₆ ishydrogen, R₂₇ and R₂₈ are each independently of the other hydrogen orC₁-C₄alkyl, R₂₉ is hydrogen, R₃₀ is hydrogen, phenyl, C₁-C₁₈alkyl;C₂-C₁₈alkyl interrupted by oxygen or by sulfur; C₇-C₉-phenylalkyl; orC₇-C₁₈phenylalkyl interrupted by oxygen or by sulfur and unsubstitutedor substituted on the phenyl radical by from 1 to 3 C₁-C₄alkyl groups,R₃₁ is hydrogen or C₁-C₄alkyl, R₃₂ is hydrogen, C₁-C₁₈alkanoyl;C₃-C₁₂alkanoyl interrupted by oxygen or by sulfur; C₂-C₁₂-alkanoylsubstituted by a di(C₁-C₆alkyl) phosphonate group;C₆-C₉cycloalkylcarbonyl,

R₃₃ is hydrogen or C₁-C₄alkyl, R₃₄ is C₁-C₁₂alkylene, C₂-C₈alkylidene,C₇-C₁₂phenylalkylidene, C₅-C₈cycloalkylene or phenylene, R₃₅is hydroxy,$\left\lbrack {{—O}^{-}\frac{1}{r}M^{r +}} \right\rbrack$

or C₁-C₁₈alkoxy, R₃₆ is oxygen or —NH—, R₃₇ is C₁-C₈alkyl or phenyl, R₄₂is hydrogen, hydroxy, C₁-C₁₈alkyl, C₇-C₉phenylalkyl, unsubstituted orC₁-C₄alkyl-substituted phenyl; C₅-C₈cycloalkyl; or C₃-C₂₅alkyl which isinterrupted by oxygen or sulfur, R₄₃ is C₁-C₁₈alkyl, C₇-C₉phenylalkyl,unsubstituted or C₁-C₄alkyl-substituted phenyl; C₅-C₈cycloalkyl; orC₃-C₁₈alkyl which is interrupted by oxygen or sulfur, R₄₄ and R₄₅ areeach independently of one another hydrogen, C₁-C₁₈alkyl,hydroxyl-substituted C₂-C₁₈alkyl; C₃-C₁₈alkyl which is interrupted byoxygen or sulfur; C₇-C₉-phenylalkyl, or C₃-C₁₈alkenyl; or R₄₄ and R₄₅,together with the nitrogen atom to which they are attached, form a6-membered heterocyclic ring, R₄₆ is C₁-C₁₈alkyl, and s is1 or2.
 4. Aprocess according to claim 1, wherein, when n is 1, R₁ is naphthyl,phenanthryl, thienyl, pyridyl, dibenzofuryl, unsubstituted orC₁-C₄alkyl-substituted carbazolyl; or fluorenyl, or R₁ is a radical offormula II

when n is 2, R₁ is phenylene or naphthylene; R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃are each independently of the others hydrogen, chloro, bromo,fluoro-substituted C₁-C₈alkyl; —CN,

hydroxy, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, C₁-C₁₈alkylthio, phenyl, benzoyl,benzoyloxy or

R₂₉ is hydrogen, R₃₀ is hydrogen, phenyl or C₁-C₁₈alkyl, R₃₁ is hydrogenor C₁-C₄alkyl, R₃₂ is hydrogen, C₁-C₁₂alkanoyl or benzoyl, and R₄₃ isC₁-C₁₈alkyl, benzyl, phenyl; cyclohexyl; or C₃-C₁₂alkyl which isinterrupted by oxygen, and R₄₄ and R₄₅ are each independently of oneanother hydrogen, C₁-C₁₄alkyl, hydroxyl-substituted C₂-C₁₄alkyl;C₃-C₁₂alkyl which is interrupted by oxygen; benzyl or C₃-C₁₂alkenyl. 5.A process according to claim 4, wherein R₁₉ is hydrogen, hydroxy, bromo,trifluoromethyl, C₁-C₄alkyl or C₁-C₄alkoxy, R₂₀ is hydrogen, bromo,trifluoromethyl, C₁-C₄alkyl or C₁-C₄alkoxy, R₂₁ is hydrogen, bromo,trifluoromethyl, C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, R₂₂ ishydrogen, bromo, trifluoromethyl, C₁-C₄alkyl or C₁-C₄alkoxy, and R₂₃ ishydrogen, hydroxy, bromo, trifluoromethyl, C₁-C₄alkyl or C₁-C₄alkoxy. 6.A process according to claim 1, wherein R₂, R₃, R₄ and R₅ are eachindependently of the others hydrogen, fluorine, hydroxy, C₁-C₂₅-alkyl,C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substituted phenyl;unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl; C₁-C,₂alkoxy,C₁-C₁₂alkylthio, C₁-C₄alkylamino, di-(C₁-C₄alkyl)amino,C₁-C₁₈alkanoyloxy, C₁-C₁₈alkanoylamino; C₃-C₁₈alkanoyloxy interrupted byoxygen, sulfur or by

C₆-C₉cycloalkylcarbonyloxy, benzoyloxy or C₁-C₈alkyl-substitutedbenzoyloxy, or furthermore the radicals R₂ and R₃ or the radicals R₃ andR₄ or the radicals R₄ and R₅, together with the carbon atoms to whichthey are bonded, form a benzo ring, R₄ is additionally —(CH₂)_(p)—COR₉or —(CH₂)_(q)OH or, when R₃ and R₅ are hydrogen, R₄ is additionally aradical of formula IV

R₈ is C₁-C₆alkyl, R₉ is hydroxy, C₁-C₁₈alkoxy or

R₁₀ and R₁₁ are methyl groups or, together with the carbon atom to whichthey are bonded, form a C₅-C₈cycloalkylidene ring unsubstituted orsubstituted by from 1 to 3 C₁-C₄alkyl groups; R₁₂ and R₁₃ are eachindependently of the other hydrogen or C₁-C₈alkyl, and q is 2, 3, 4, 5or
 6. 7. A process according to claim 1, wherein at least two of theradicals R₂, R₃, R₄ and R₅ are hydrogen.
 8. A process according to claim1, wherein R₃ and R₅ are hydrogen.
 9. A process according to claim 1,wherein R₂, R₃, R₄ and R₅ are each independently of the others hydrogen,fluorine, hydroxy, C₁-C₁₈-alkyl, C₇-C₉phenylalkyl, phenyl,C₅-C₈cycloalkyl, C₁-C₆alkoxy, cyclohexylcarbonyloxy or benzoyloxy, orfurthermore the radicals R₂ and R₃ or the radicals R₃ and R₄ or theradicals R₄ and R₅, together with the carbon atoms to which they arebonded, form a benzo ring, R₄ is additionally —(CH₂)_(p)—COR₉, or, whenR₃ and R₅ are hydrogen, R₄ is additionally a radical of formula IV, R₉is hydroxy or C₁-C₁₈alkoxy, and R₁₀ and R₁₁ are methyl groups or,together with the carbon atom to which they are bonded, form aC₅-C₈cycloalkylidene ring.
 10. A process according to claim 1, whereinR₂ is C₁-C₁₈alkyl or cyclohexyl, R₃ is hydrogen, R₄ is C₁-C₄alkyl,cyclohexyl, —(CH₂)_(p)—COR₉ or a radical of formula IV, R₅ is hydrogen,R₉ is C₁-C₄alkyl, R₁₀ and R₁₁, together with the carbon atom to whichthey are bonded, form a cyclohexylidene ring, and p is
 2. 11. A processaccording to claim 1, wherein the aqueous solvent is an aqueous alcohol.12. A process for the preparation of compounds of formula I

wherein the general symbols are as defined in claim 1, which processcomprises converting a compound of formula VlI

wherein R₁ and n are as defined in claim 1, R₂, R₃, R″₄ and R₅ are eachindependently of the others hydrogen, fluorine, hydroxy, C₁-C₂₅-alkyl,C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substituted phenyl,unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl; C₁-C₁₈alkoxy,C₁-C₁₈alkylthio, C₁-C₄alkylamino, di(C₁-C₄alkyl)amino,C₁-C₂₅alkanoyloxy, C₁-C₂₅alkanoylamino; C₃-C₂₅alkanoyloxy interrupted byoxygen, sulfur or by

C₆-C₉cycloalkylcarbonyloxy, benzoyloxy or C₁-C₁₂alkyl-substitutedbenzoyloxy, or furthermore the radicals R₂ and R₃ or the radicals R₃ andR″₄ or the radicals R″₄ and R₅, together with the carbon atoms to whichthey are bonded, form a benzo ring, R″₄ is additionally —(CH₂)_(p)—COR₉or —(CH₂)_(q)OH or, when R₃ and R₅ are hydrogen, R″₄ is additionally aradical of formula VIII

wherein R₁ is as defined in claim 1 for the case where n=1, R₂, R₁₀ andR₁₁ are as defined in claim 1, R₅₀ is —OR₅₁, —SR₅₂,

R₅₁ is C₁-C₂₅alkyl; C₂-C₂₅alkyl interrupted by oxygen or by sulfur;C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; unsubstituted or C₁-C₄alkyl-substituted phenyl, R₅₂ isC₁-C₂₅alkyl; C₂-C₂₅alkyl interrupted by oxygen or by sulfur;C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; unsubstituted or C₁-C₄alkyl-substituted phenyl, R₅₃ andR₅₄ are each independently of the other hydrogen, C₁-C₂₅ alkyl;C₂-C₂₅alkyl interrupted by oxygen or by sulfur; C₇-C₉phenylalkyl,unsubstituted or C₁-C₄alkyl-substituted C₅-C₈-cycloalkyl; or adendrimeric, oligomeric or polymeric C₄-C₁₀₀hydrocarbon radical, R₅₅ isC₁-C₂₅alkyl; C₂-C₂₅alkyl interrupted by oxygen or by sulfur;C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; unsubstituted or C₁-C₄alkyl-substituted phenyl; or aradical of formula IX

wherein R₁ and n are as defined in claim 1, R₅₆ is unsubstituted orC₁-C₄alkyl-substituted C₂-C₁₂alkylene, with an aqueous cyanide saltsolution to form a compound of formula V

wherein the general symbols are as defined in claim 1, and thenhydrolyzing the compound of formula V in an aqueous solvent in thepresence of an acid.
 13. A process according to claim 12, wherein R₅₀ is—OR₅₁, —SR₅₂,

R₅₁, is C₁-C₁₂alkyl; C₂-C₁₂alkyl interrupted by oxygen; benzyl,C₅-C₈cycloalkyl or phenyl, R₅₂ is C₁-C₁₂alkyl; C₂-C₁₂alkyl interruptedby oxygen; benzyl, C₅-C₈cycloalkyl or phenyl, R₅₃ and R₅₄ are eachindependently of the other hydrogen, C₁-C₁₂alkyl; C₂-C₁₂alkylinterrupted by oxygen; benzyl, C₅-C₈cycloalkyl, or a dendrimeric oroligomeric or polymeric C₄-C₅₀hydrocarbon radical, R₅₅ is C₁-C₁₂alkyl;C₂-C₁₂alkyl interrupted by oxygen; benzyl, C₅-C₈cycloalkyl, phenyl or aradical of formula IX

wherein R₁ and n are as defined in claim 1, and R₅₆ is C₂-C₈alkylene.14. A process according to claim 12, wherein R₅₀ is

R₅₃ and R₅₄ are each independently of the other hydrogen, C₁-C₁₂alkyl,benzyl, cyclohexyl or a dendrimeric C₄-C₃₀hydrocarbon radical, R₅₅ isC₁-C₁₂alkyl, benzyl, cyclohexyl, phenyl or a radical of formula IX

wherein R₁ and n are as defined in claim 1, and R₅₆ is C₄-C₈alkylene.15. A process according to claim 12, wherein R₅₀ is

R₅₃ and R₅₄ are each independently of the other C₁-C₁₂alkyl, benzyl or adendrimeric C₄-C₃₀hydrocarbon radical, and R₅₆ is C₄-C₆alkylene.
 16. Aprocess according to claim 12, wherein the cyanide salt is an alkalimetal cyanide salt.
 17. A compound of formula V

wherein, when n is 1, R₁ is naphthyl, phenanthryl, anthryl,5,6,7,8-tetrahydro-2-naphthyl, thienyl, benzo[b]thienyl,naphtho[2,3-b]thienyl, thianthrenyl, furyl, benzofuryl, isobenzofuryl,dibenzofuryl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl,pyrazolyl, pyrazinyl, pyridyl, pyrimidinyl, pyridazinyl, indolizinyl,isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl,quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl,cinnolinyl, pteridinyl, carbazolyl, β-carbolinyl, phenanthridinyl,acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl,phenothiazinyl, isoxazolyl, furazanyl, biphenyl, terphenyl, fluorenyl orphenoxazinyl, each of which is unsubstituted or substituted by fluorine,hydroxy, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, C₁-C₁₈alkylthio,di-(C₁-C₄alkyl)amino, phenyl, benzyl, benzoyl or by benzoyloxy or R₁ isa radical of formula II or III

when n is 2, R₁ is phenylene or naphthylene each unsubstituted orsubstituted by C₁-C₄alkyl or by fluorine; or is —R₆—X—R₇—, R₂, R₃, R′₄and R₅ are each independently of the others hydrogen, fluorine, hydroxy,C₁-C₂₅-alkyl, C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substitutedphenyl, unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl;C₁-C₁₈alkoxy, C₁-C₁₈alkylthio, C₁-C₄alkylamino, di-(C₁-C₄alkyl)amino,C₁-C₂₅alkanoyloxy, C₁-C₂₅alkanoylamino; C₃-C₂₅alkanoyloxy interrupted byoxygen, sulfur or by

C₆-C₉cycloalkylcarbonyloxy, benzoyloxy or C₁-C₁₂alkyl-substitutedbenzoyloxy, or furthermore the radicals R₂ and R₃ or the radicals R₃ andR′₄ or the radicals R′₄ and R₅, together with the carbon atoms to whichthey are bonded, form a benzo ring, R′₄ is additionally —(CH₂)_(p)—COR₉or —(CH₂)_(q)OH or, when R₃ and R₅ are hydrogen, R′₄ is additionally aradical of formula VI

wherein R₁ is as defined above for the case where n=1, R₆ and R₇ areeach independently of the other phenylene or naphthylene eachunsubstituted or substituted by C₁-C₄alkyl, R₈ is C₁-C₈alkyl, R₉ ishydroxy, $\left\lbrack {{—O}^{-}\frac{1}{r}M^{r +}} \right\rbrack,$

C₁-C₁₈alkoxy or

R₁₀ and R₁₁ are each independently of the other hydrogen, CF₃,C₁-C₁₂alkyl or phenyl, or R₁₀ and R₁₁ together with the carbon atom towhich they are bonded, form a C₅-C₈cycloalkyl-idene ring unsubstitutedor substituted by from 1 to 3 C₁-C₄alkyl groups; R₁₂ and R₁₃ are eachindependently of the other hydrogen or C₁-C₁₈alkyl, R₁₄ is hydrogen orC₁-C₁₈alkyl, R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ are each independently of theothers hydrogen, halogen, fluoro-substituted C₁-C₁₂alkyl; —CN,

—SOR₄₆, —SO₂R₄₆, SO₃R₄₆, hydroxy, C₁-C₂₅alkyl; C₂-C₂₅alkyl interruptedby oxygen, sulfur or by

C₁-C₂₅alkoxy; C₂-C₂₅alkoxy interrupted by oxygen, sulfur or by

C₁-C₂₅alkylthio, C₇-C₉phenylalkyl, C₇-C₉phenylalkoxy, unsubstituted orC₁-C₄alkyl-substituted phenyl; unsubstituted or C₁-C₄alkyl-substitutedphenoxy; unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl;unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkoxy;di(C₁-C₄alkyl)amino, C₁-C₂₅alkanoyl; C₃-C₂₅alkanoyl interrupted byoxygen, sulfur or by

C₁-C₂₅alkanoyloxy; C₃-C₂₅alkanoyloxy interrupted by oxygen, sulfur or by

C₁-C₂₅alkanoylamino, C₆-C₉cycloalkylcarbonyl,C₆-C₉cycloalkylcarbonyloxy, benzoyl or C₁-C₁₂alkyl-substituted benzoyl;benzoyloxy or C₁-C₁₂alkyl-substituted benzoyloxy;

R₂₄ is hydrogen, C₁-C₄alkyl, or unsubstituted or C₁-C₄alkyl-substitutedphenyl, R₂₅ and R₂₆ are hydrogen, C₁-C₄alkyl or phenyl, with the provisothat at least one of the radicals R₂₅ and R₂₆ is hydrogen, R₂₇ and R₂₈are each independently of the other hydrogen, C₁-C₄alkyl or phenyl, R₂₉is hydrogen or C₁-C₄alkyl, R₃₀ is hydrogen, unsubstituted orC₁-C₄alkyl-substituted phenyl; C₁-C₂₅alkyl; C₂-C₂₅alkyl interrupted byoxygen, sulfur or by

C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl radical byfrom 1 to 3 C₁-C₄alkyl groups; or C₇-C₂₅phenylalkyl interrupted byoxygen, sulfur or by

and unsubstituted or substituted on the phenyl radical by from 1 to 3C₁-C₄alkyl groups, R₃₁ is hydrogen or C₁-C₄alkyl, R₃₂ is hydrogen,C₁-C₂₅alkanoyl; C₃-C₂₅alkanoyl interrupted by oxygen, sulfur or by

C₂-C₂₅alkanoyl substituted by a di(C₁-C₆alkyl) phosphonate group;C₆-C₉cycloalkylcarbonyl, thenoyl, furoyl, benzoyl, orC₁-C₁₂alkyl-substituted benzoyl;

R₃₃ is hydrogen or C₁-C₈alkyl, R₃₄ is a direct bond, C₁-C₁₈alkylene;C₂-C₁₈alkylene interrupted by oxygen, sulfur or by

C₂-C₂₀alkylidene, C₇-C₂₀phenylalkylidene, C₅-C₈cycloalkylene,C₇-C₈bicycloalkylene, unsubstituted or C₁-C₄alkyl-substituted phenylene,

R₃₅ is hydroxy,$\left\lbrack {{—O}^{-}\frac{1}{r}M^{r +}} \right\rbrack,$

C₁-C₁₈alkoxy or

R₃₆ is oxygen, —NH— or

R₃₇ is C₁-C₁₈alkyl or phenyl, R₄₂ is hydrogen, hydroxy,$\left\lbrack {{—O}^{-}\frac{1}{r}M^{r +}} \right\rbrack,$

C₁-C₂₅alkyl, C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substitutedphenyl; unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl; orC₃-C₂₅alkyl which is interrupted by oxygen, sulfur or

R₄₃ is C₁-C₂₅alkyl, C₇-C₉phenylalkyl, unsubstituted orC₁-C₄alkyl-substituted phenyl; unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; or C₃-C₂₅alkyl which is interrupted by oxygen, sulfuror

R₄₄ and R₄₅ are each independently of one another hydrogen, C₁-C₂₅alkyl,hydroxyl-substituted C₂-C₂₄alkyl; C₃-C₂₅alkyl which is interrupted byoxygen, sulfur or

phenylalkyl which is unsubstituted or is substituted on the phenyl ringby C₁-C₄alkyl; or C₃-C₂₄alkenyl; or R₄₄ and R₄₅, together with thenitrogen atom to which they are attached, form a 5-, 6- or 7-memberedheterocyclic ring which is unsubstituted or is substituted by C₁-C₄alkylor is interrupted by oxygen, sulfur or

R₄₆ is hydrogen or C₁-C₂₅alkyl, M is an r-valent metal cation, X is adirect bond, oxygen, sulfur or —NR₁₄—, n is 1 or 2, p is 0, 1 or 2, q is1,2,3,4,5 or6, r is 1, 2 or 3, and s is 0, 1 or 2; with the provisothat, when R₂, R₃, R₅, R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ are hydrogen, R′₄ isnot methylthio.
 18. A composition comprising a) an organic materialwhich is susceptible to oxidative, thermal or light-induced degradation,and b) at least one compound of the formula V according to claim
 17. 19.A composition according to claim 18, wherein component (a) is selectedfrom the group consisting of a lubricant, a fuel, a hydraulic fluid, ametal-working fluid and a natural, semi-synthetic or synthetic polymer.20. A composition according to claim 18, comprising as component (a) anengine oil, a turbine oil, a gear oil, a diesel fuel or a lubricatinggrease.
 21. A composition according to claim 18, comprising as component(a) a synthetic polymer.
 22. A composition according to claim 18,wherein component (b) is present in an amount of from 0.0005 to 10%,based on the weight of component (a).
 23. A composition according toclaim 18, comprising in addition, besides components (a) and (b),further additives.
 24. A composition according to claim 23, comprisingas further additives phenolic antioxidants, light-stabilizers and/orprocessing stabilizers.
 25. A process for stabilizing an organicmaterial against oxidative, thermal or light-induced degradation, whichcomprises incorporating therein or applying thereto at least onecompound of the formula V according to claim 17.